U.S. patent number 9,637,615 [Application Number 14/032,445] was granted by the patent office on 2017-05-02 for preparation and uses of bio-adhesives.
This patent grant is currently assigned to North Carolina Agricultural and Technical State University. The grantee listed for this patent is North Carolina Agricultural and Technical State University. Invention is credited to Elham H. Fini.
United States Patent |
9,637,615 |
Fini |
May 2, 2017 |
Preparation and uses of bio-adhesives
Abstract
The present application relates generally to bio-adhesive
components isolated from bio-oil prepared from animal waste,
methods of preparation of the bio-adhesive components and uses
thereof. Such uses include, but are not limited to, asphalt
bio-binders, bio-adhesion promoters, asphalt bio-rejuvenators,
asphalt bio-extenders, bio-asphalt as well as uses in roofing, soil
stabilization, crack and joint sealing and flooring adhesives.
Inventors: |
Fini; Elham H. (Asheboro,
NC) |
Applicant: |
Name |
City |
State |
Country |
Type |
North Carolina Agricultural and Technical State University |
Greensboro |
NC |
US |
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Assignee: |
North Carolina Agricultural and
Technical State University (Greensboro, NC)
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Family
ID: |
50337605 |
Appl.
No.: |
14/032,445 |
Filed: |
September 20, 2013 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20140083331 A1 |
Mar 27, 2014 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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61782547 |
Mar 14, 2013 |
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61704175 |
Sep 21, 2012 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01D
3/10 (20130101); B01D 3/40 (20130101); C08K
11/005 (20130101); C09D 191/00 (20130101); E01C
7/35 (20130101); C08L 95/00 (20130101); C09D
195/00 (20130101); C09D 195/00 (20130101); C08L
91/00 (20130101); C08L 95/00 (20130101); C08L
91/00 (20130101); C08L 2555/64 (20130101); E01C
7/262 (20130101); Y02A 30/333 (20180101); Y02A
30/30 (20180101) |
Current International
Class: |
C08L
95/00 (20060101); C09D 191/00 (20060101); C09D
195/00 (20060101); B01D 3/40 (20060101); B01D
3/10 (20060101); C08K 11/00 (20060101); C08L
91/00 (20060101); E01C 7/35 (20060101); E01C
7/26 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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WO 2014/047462 |
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Mar 2014 |
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WO |
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Other References
Fini et al, "Chemical Characterization of Biobinder form Swine
Manure: Sustainable modifier for asphalt binder", Journal of
Materials in Civil Engineering (Nov. 2011) pp. 1506-1513. cited by
examiner .
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Transporation Research Board (Aug. 2012). cited by examiner .
Fini et al., "Application of Swine Manure in Development of
Bio-Adhesive," Allen D. Leman Swine Conference, p. 244 (Sep. 18,
2012). cited by applicant .
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Separated by Molecular Distillation," Applied Energy, vol. 87, No.
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applicant .
Fini et al., "Chemical Characterization of Biobinder from Swine
Manure: A Sustainable Modifier for Asphalt Binder," Journal of
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(2011). cited by applicant .
Fini et al., "Partial Replacement of Asphalt Binder with
Bio-Binder: Characterization and Modification," International
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Fini, E.H., and Abu-Lebdeh, T., "Bonding Property of Bituminous
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Warm-Mix Asphalt, Extracted and Recovered RAP and RAS, and
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Use in Asphalt Pavements," ICSDEC 2012 Developing the Frontier of
Sustainable Design, Engineering, and Construction, ASCE, pp. 1-13
(2012). cited by applicant .
Fini et al., "Characterization and Application of Manure-Based
Bio-binder in Asphalt Industry," Paper No. 10-2871 The 89th
Transportation Research Board Annual Meetings, Washington, D.C., 14
pages (Jan. 2010). cited by applicant .
Fini, E.H., and Al-Qadi, I.L., "Development of Pressurized Blister
Test for Interface Characterization of Aggregate--Highly
Polymerized Bituminous Materials," ASCE Journal of Materials,
American Society of Civil Engineering (ASCE). vol. 23, No. 5 pp.
656-663 (2011). cited by applicant .
Fini, E.H., and Beuhler, M.J., "Reducing Asphalt's Low Temperature
Cracking by Disturbing its Crystallization," 7th RILEM
International Conference on Cracking in Pavements Jun. 20-22, 2012
in Delft, Netherlands, RILEM Bookseries vol. 4, pp. 911-919 (2012).
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Hill et al., "Low-Temperature Performance Characterization of
Biomodified Asphalt Mixtures That Contain Reclaimed Asphalt
Pavement," Transportation Research Record: Journal of the
Transportation Research Board 2371, pp. 49-57 (2013). cited by
applicant .
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Bio-Modified Asphalt Mixtures," Paper No. 12-2411, the 91st
Transportation Research Board Annual Meetings, Washington, D.C.,
pp. 1-16 (Jan. 2012). cited by applicant .
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Treaty) corresponding to International Patent Applciation No.
PCT/US2013/060968 dated Apr. 2, 2015. cited by applicant .
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Using a Continuous Reactor System: Effects of Operating Parameters
on Oil Yield and Quality," Transactions of the ASABE. vol. 49, No.
6 pp. 1897-1904 (2006). cited by applicant .
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of swine manure into oil using a continuous reactor system:
Development and testing." Transactions--American Society of
Agricultural Engineers, 49(2), 533-541 (2006). cited by applicant
.
Onochie et al., "Rheological Characterization of Nano-particle
based Bio-modified Binder," Transportation Research Board 92nd
Annual Meeting, Washington, D.C., 16 pages (2013). cited by
applicant .
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Evalulation Summary, pp. 1-2 (Aug. 2011). cited by applicant .
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www.epa.gov/oecaagct/ag101/printpoultry.html; last updated Jun. 27,
2012; pp. 1-32. cited by applicant .
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of Value 2012 Summary," United States Department of Agriculture,
National Agricultural Statistics Serivice, 14 pages (Apr. 2013).
cited by applicant .
He, "Rheological Hybrid Effect and its Conditions in Filled Polymer
Melts," Macromol. Symp., 277, pp. 43-50 (2009). cited by applicant
.
Mi et al., "Rheological Hybrid Effect in Dually Filled
Polycarbonate Melt Containing Liquid Crystalline Polymer," Polymer
Engineering and Science, DOI 10.1002/pen, pp. 289-299 (2012). cited
by applicant .
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Continuous Reactor System," Dissertation, University of Illinois at
Urbana-Champaign, AAT 3202149, pp. iii-183 (Sep. 22, 2005). cited
by applicant .
Yero et al., "Viscosity Characteristics of Modified Bitumen," ARPN
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2012). cited by applicant.
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Primary Examiner: Brunsman; David M
Attorney, Agent or Firm: Jenkins, Wilson, Taylor &
Hunt
Government Interests
STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED
RESEARCH OR DEVELOPMENT
Work described herein may have been supported in part by NSF I-Corp
(IIP-1246330), NSF Career (CMMI-1150695) CBET-1040246, CBET-0923425
and NSF EAGER (0955001). The United States Government may therefore
have certain rights in the inventions.
Parent Case Text
RELATED APPLICATIONS
This application claims priority under 35 U.S.C. .sctn.119(e) to
U.S. Provisional Patent Application Ser. Nos. 61/782,547, filed
Mar. 14, 2013, and 61/704,175, filed Sep. 21, 2012, the disclosure
of each of which is incorporated herein by reference in its
entirety.
FIELD
The present inventions relate generally to bio-adhesive components
isolated from bio-oil prepared from animal waste, methods of
preparation of the bio-adhesive components and uses thereof.
Claims
What is claimed:
1. A method of isolating a bio-adhesive composition from a bio-oil,
the method comprising: (a) providing a bio-oil derived from animal
waste; (b) distilling the bio-oil to remove a light liquid fraction
and provide a pot liquor, such that the viscosity of the pot liquor
is not allowed to exceed about 1 centipoise (cP) at 135.degree. C.,
wherein the distilling occurs at a vacuum pressure of between about
1 mm Hg and about 80 mm Hg while heating to a temperature of up to
60.degree. C.; and (I) isolating the pot liquor to provide a
bio-adhesive composition comprising a heavy liquid fraction and a
bio-residue; or (II) continuing to distill the pot liquor to
provide a distilled heavy liquid fraction and a bio-residue that is
not distilled, wherein the viscosity of the bio-residue is not
allowed to exceed about 1 cP at 135.degree. C., wherein the
distilling occurs under vacuum pressure of between about 1 mm Hg
and about 80 mm Hg while heating to (1) a temperature ranging from
about 60.degree. C. to about 100.degree. C., or (2) a temperature
ranging from about 100.degree. C. to about 160.degree. C., and
isolating a bio-adhesive composition comprising the distilled heavy
liquid fraction from (1) and/or (2).
2. The method of claim 1, where the animal waste comprises beef
manure, dairy manure, swine manure, sheep manure, poultry manure or
combinations thereof.
3. The method of claim 2, wherein the animal waste comprises swine
manure, and in (b) the vacuum pressure is between about 1 mm Hg and
about 40 mm Hg and the rate of heating is between about 5.degree.
C. per hour and about 50.degree. C. per hour while heating up to a
temperature of 60.degree. C.
4. The method of claim 3, wherein in (b) the vacuum pressure is
about 3 mm Hg and the rate of heating is between about 15.degree.
C. per hour and about 30.degree. C. per hour while heating up to a
temperature of 60.degree. C.
5. The method of claim 2, where the animal waste comprises swine
manure.
6. The method of claim 5, where the swine manure comprises at least
about 30% solid manure.
7. The method of claim 1, wherein the viscosity of the pot liquor
is not allowed to exceed 0.5 cP at 135.degree. C.
8. The method of claim 1, further comprising combining the isolated
bio-adhesive composition of (I) or (II) with bitumen, asphalt
binder, nanoclay, rubber, or petroleum-based asphalt.
9. The method of claim 8, wherein the isolated bio-adhesive
composition of (II) is combined with bitumen.
10. The method of claim 1, further comprising (III) isolating the
bio-residue to provide a bio-adhesive composition.
11. The method of claim 10, wherein the viscosity of the
bio-residue of (II) is not allowed to exceed 0.5 cP at 135.degree.
C.
12. The method of claim 10, further comprising combining the
bio-adhesive composition comprising the isolated bio-residue with
bitumen, asphalt.
13. The method of claim 1, wherein the temperature in (II) ranges
from about 60.degree. C. to about 100.degree. C. and the isolated
bio-adhesive composition comprises a distilled heavy liquid
fraction comprising at least about 5% by weight of amide-containing
compounds.
14. The method of claim 1, wherein the temperature in (II) ranges
from about 100.degree. C. to about 160.degree. C. and the isolated
bio-adhesive composition comprises a distilled heavy liquid
fraction comprising up to about 5% by weight of amide-containing
compounds.
15. The method of claim 1, wherein the animal waste comprises swine
manure, and in (II) the vacuum pressure is between about 1 mm Hg
and about 40 mm Hg and the rate of heating is between about
5.degree. C. per hour and about 50.degree. C. per hour.
16. The method of claim 1, wherein the viscosity of the isolated
bio-adhesive composition is not allowed to exceed 0.5 cP at
135.degree. C.
Description
BACKGROUND
According to the USDA, "the combined value of production from
broilers, eggs, turkeys, and the value of sales from chickens in
2011 was $35.6 billion . . . . Of the combined total, 65 percent
was from broilers, 21 percent from eggs, 14 percent from turkeys,
and less than 1 percent from chickens." (USDA, National
Agricultural Statistics Service "Poultry--Production and Value 2011
Summary" (April 2012)) According to the US EPA the composition of
solid manure from pullets and laying hens in layer cages can range
in dry matter between 20% and 60% and semi-solid manure contains 12
to 20% solids. (US EPA|Ag 101|Poultry Production,
www.epa.gov/oecaagct/ag101/printpoultry.html). Poultry manure is
typically used in surface applications to croplands.
Within the United States, pork production is a major agricultural
enterprise; specifically, a gross income of roughly $16 billion
resulted from the sale of 116 million pigs in 2008. In general,
pigs weighing 21 to 100 kg generate 0.39 to 0.45 kg of waste per
day per pig on a dry matter basis. Swine manure is usually disposed
of by storage in lagoons. This process has significant negative
environmental impacts, particularly with respect to surface water
and groundwater quality as well as air quality, which is affected
by odors and gaseous emissions.
Dairy and beef production are similarly important components of
U.S. agricultural efforts. Removal or treatment of animal waste is
analogously a key consideration as the number of cows raised in the
U.S. trends upwards.
To improve the ultimate processing of beef, dairy, poultry, sheep
and swine manure, researchers have developed methods to convert
manure to gas and/or oil. Collection of manure is easier in
confined animal feeding operations, due in part to bulk processing
of waste, as well as the controlled diet of the animals. Bio-oil
produced from animal waste is an energy-dense crude oil that is
similar to petroleum extracts. By-products of bio-oil produced from
animal waste include an aqueous phase and a solid phase; uses for
both by-products have been identified in the art.
Petroleum-based products, such as adhesives, are used in pavement
construction as asphalt binders, adhesion promoters, asphalt
extenders and asphalt concrete. In addition they are used in
roofing, soil stabilization, crack and joint sealing and as
flooring adhesives.
The U.S. asphalt market is valued at approximately $11.7
billion/year. Asphalt supplies are shrinking, while the demand for
it is increasing rapidly. As the price of asphalt increases, the
demand for alternative and renewable resources increases.
The trend toward sustainable pavements has led the pavement
industry to emphasize use of recycled materials, including rubber
from tires and fly ash as well as reclaimed asphalt pavement (RAP)
and recycled asphalt shingles (RAS) in pavement construction. Use
of these recycled products reduces the environmental liability of
RAP and RAS and further reduces the amount of virgin asphalt used
in pavement construction. In the U.S., about 100 million tons of
RAP and 11 million tons of RAS are produced annually. Because
asphalt in both RAP and RAS is much stiffer than virgin asphalt,
inclusion of RAP and/or RAS lead to a significant increase in the
stiffness of the resulting recycled-asphalt mixture. Stiff asphalt
mixtures have been shown to be hard to place and susceptible to
cracking a lower temperatures. Addressing these factors is an
important challenge to the use of high percentages of RAP and RAS
in pavement construction.
Hot-mix asphalt production is the most common paving approach in
the United States; however, concerns about the process's
environmental pollution continue to grow because of the emission of
greenhouse gases during the construction of hot-mix pavement. To
address these concerns, a new group of technologies has been
developed for asphalt pavement production. These technologies,
called warm mix asphalt (WMA), allow producers of asphalt pavement
material to lower the temperatures at which the material is mixed
and placed on the road. Reductions of 50.degree. F. to 100.degree.
F. have been observed. Reducing production temperature results in
reduced fuel consumption as well as reduced greenhouse emissions,
and improves job site conditions for workers. Lower production
temperature also reduces the initial aging of the binder, which can
improve long-term durability and pavement performance. To produce
WMA, several different technologies and additives have been used
along with asphalt binder to reduce viscosity of the binder.
However, most of these additives are petroleum-based and
costly.
Despite the large market for scrap tires, roughly a quarter of all
scrap tires end up in landfills each year numbering to
approximately 27 million tires or roughly 6 million tons annually
making up over 12% of all solid waste. Due to cross-linking between
the rubber polymer chains, numerous additives, and stabilizers
within its structure, rubber is extremely resistant to natural
degradation making it troublesome for landfill storage. Crumb
rubber's use in asphalt binder and pavements provides an
environmentally sustainable method for disposing the millions of
tires generated annually. Generally, tires are ground using ambient
or cryogenic means, the goal of which is to reduce the size of the
rubber into a fine powder of particle sizes smaller than 2 mm in
diameter. The rubber can be used in a variety of uses, including a
modifier for petroleum-based asphalt binder. The modification of
asphalt mixture with rubber is typically classified into three
different methods: (a) Dry Process, which uses crumb rubber as an
aggregate substitute; (b) Wet Process with Agitation, in which
large particles (particles not passing No. 50 Sieve) are blended
with the binder while applying agitation during mixing to keep
crumb rubber particles uniformly distributed; and (c) Wet Process
with no Agitation, in which small particles (passing No. 50 Sieve)
are blended with asphalt binder with no agitation.
One important variable in asphalt concrete pavements is adhesion
between aggregate and asphalt/bitumen. Adhesion promoters, also
known as anti-strips, are used to improve the interaction between
asphalt and the aggregates comprising asphalt concrete. Changes to
the use of asphalt concrete pavements and advances in technology
have led to an increased need for adhesion promoters of particular
characteristics. In particular, users are looking for asphalt
pavements having longer lifespans, but over which the pavements
will be subjected to increasing traffic loads. Adhesion promoters
are used for a variety of goals, including by not limited to
mitigating and inhibiting the damaging effects of moisture in
asphalt pavements. Water damage is manifest in a number of ways,
which can lead to potholes, for example, freeze-thaw cycles
exacerbate the effect of water damage. On the molecular level the
result of water damage is the loss of adhesion between the binder
and the aggregate, also known as stripping. The majority of current
adhesion promoters are petroleum-based and suffer from increasing
demand and correspondingly cost, while supplies are shrinking. A
source of non-petroleum based adhesion promoters is needed in the
industry.
Asphalt rejuvenators are generally used to restore the balance
between maltenes and asphaltenes in asphalt binder that has been
disturbed over time due to progressive aging. Because of weathering
or oxidation, the ratio of maltenes to asphaltenes is changed as
some of the maltenes compounds are transformed to asphaltenes
component over time. The effectiveness of a rejuvenator is
typically evaluated by whether it can restore the
maltene/asphaltene balance; targeted rejuvenators usually contain
maltenes-type fractions to improve and balance the maltenes to
asphaltenes ratio. To evaluate its effectiveness as a rejuvenator a
test method, including but not limited to asphalt penetration,
viscosity, or abrasion loss test are used.
Asphalt rejuvenators are usually formulated to revive an aging
pavement, improving the composition of the asphalt cement and
increase penetration value of the asphalt cement in the top portion
of the pavement thereby increasing the durability and lifespan of
the pavement and to seal pavement against air and water, thereby
slowing oxidative degradation. Typically, rejuvenators are used on
asphalt pavement to stop and/or reverse shrinking which can lead to
hairline cracking, to inhibit pitting and raveling, and to reduce
air and water permeability, which can lead to pavement degradation.
Asphalt rejuvenators can be used in asphalt rehabilitation as well
as hot-in place and cold-in place recycling.
Asphalt extenders are generally petroleum-based products enabling
the recycling of asphalt waste, such as RAP, RAS, as well as
natural asphalt sources such as rock asphalt, tar sands, Gilsonite,
and Trinidad Lake Asphalt. Asphalt extenders enable a larger amount
of asphalt waste material to be used in a performance grade asphalt
mix, thereby reducing the cost of the performance grade asphalt mix
having the targeted mechanical and physical properties. Alternate
sources of asphalt extenders are needed in the industry, particular
as petroleum sources become ever more expensive and continue to
raise environmental concerns.
The above-identified needs in the asphalt industry have motivated
several unsuccessful attempts by researchers to produce bio-asphalt
from various materials (sugar, molasses, potato starches, vegetable
oils, lignin, cellulose, palm oil waste, coconut waste, and dried
sewage). However, those bio-asphalts either found not to be
feasible or never reached the asphalt market due to low performance
or high production cost.
Thus, there remains a need for non-petroleum based asphalt that can
be used in pavement construction. In particular, there is a need
for asphalt bio-binders, bio-adhesion promoters, asphalt
bio-rejuvenators, asphalt bio-extenders as well as bio-asphalt. In
addition, there is a need for bio-adhesives that can be used
roofing, soil stabilization, crack and joint sealing and as
flooring adhesives.
SUMMARY
The present application is generally directed to the production of
bio-adhesives having targeted viscosities. As disclosed herein,
bio-adhesive components can be prepared from a bio-oil isolated
from animal waste, including but not limited to beef, dairy, swine,
poultry, sheep manures or combinations thereof.
In one aspect, the present application discloses a method of
isolating a bio-adhesive composition from a bio-oil, the method
comprising: (a) providing a bio-oil derived from animal waste; (b)
distilling the bio-oil to remove a light liquid fraction, wherein
the distilling occurs at a vacuum pressure of between about 1 mm Hg
and about 80 mm Hg while heating to a temperature of up to about
60.degree. C., optionally wherein the rate of the heating is
between about 5.degree. C. per hour and about 50.degree. C. per
hour; and (c) isolating a bio-adhesive composition from the bio-oil
under conditions such that the viscosity of the bio-adhesive
composition is not allowed to exceed about 1 centipoise (cP) at
135.degree. C., optionally wherein the viscosity of the
bio-adhesive composition is not allowed to exceed about 0.5 cP at
135.degree. C.
In another aspect, the present application discloses a method of
isolating a bio-adhesive composition from a bio-oil, the method
comprising: (a) providing a bio-oil derived from animal waste; (b)
distilling the bio-oil to provide a distilled heavy liquid fraction
and a bio-residue that is not distilled, wherein the distilling
occurs under vacuum pressure, optionally of between about 1 mm Hg
and about 80 mm Hg, while heating to (1) a temperature ranging from
about 60.degree. C. to about 100.degree. C., or (2) a temperature
ranging from about 100.degree. C. to about 160.degree. C., wherein
the viscosity of the bio-residue is not allowed to exceed about 1
cP at 135.degree. C., optionally wherein the viscosity of the
bio-residue is not allowed to exceed about 0.5 cP at 135.degree. C.
and further optionally wherein the rate of the heating is between
about 5.degree. C. per hour and about 50.degree. C. per hour; and
(c) isolating the bio-adhesive composition comprising the heavy
liquid fraction.
In yet another aspect the present application discloses a
bio-adhesive composition produced by any method disclosed
herein.
In one aspect, the present application discloses a bio-adhesive
composition comprising a heavy liquid fraction and a bio-residue,
wherein the composition has a viscosity of at least about 0.5 cP at
135.degree. C., optionally between about 0.5 cP and about 1 cP at
135.degree. C. wherein said heavy liquid fraction and bio-residue
are isolated from bio-oil produced from animal waste and wherein
said bio-adhesive composition does not contain a light liquid
fraction.
In another aspect, the present application discloses a bio-adhesive
composition comprising a heavy liquid fraction having a viscosity
of between about 0.1 cP and 0.5 cP at 135.degree. C., optionally,
between about 0.2 cP and about 0.5 cP, wherein said bio-adhesive
composition does not contain a light liquid fraction and wherein
said heavy liquid fraction is isolated from bio-oil produced from
animal waste.
In one variation, the bio-adhesive composition comprises (a) a
heavy liquid fraction comprising at least about 5% by weight of
amide-containing compounds, optionally containing about 10% to
about 20% by weight of amide-containing compounds, or (b) a heavy
liquid fraction comprising up to about 5% by weight of
amide-containing compounds, optionally about 1% to about 5% by
weight of amide-containing compounds, wherein said bio-adhesive
composition does not contain a light liquid fraction.
In another variation, the present application discloses a
bio-adhesive composition comprising a bio-residue having a
viscosity of at least about 0.4 cP, optionally between about 0.5 cP
and 1 cP, at 135.degree. C., wherein said bio-adhesive composition
does not contain a light liquid fraction and wherein said
bio-residue is isolated from bio-oil produced from animal
waste.
In yet another variation, the present application discloses a
bio-adhesion promoter comprising a bio-adhesive composition
disclosed herein, optionally wherein the bio-adhesive composition
comprises at least about 5% by weight amide-containing compounds.
In another variation, the present application discloses an asphalt
bio-extender comprising a bio-adhesive composition as disclosed
herein optionally in combination with an asphalt binder. In one
variation, the present application discloses a bio-rejuvenator for
asphalt compositions, the bio-rejuvenator comprising a bio-adhesive
composition as disclosed herein, optionally in combination with an
asphalt binder. The present application also discloses a
bio-modified binder comprising a bio-adhesive composition disclosed
herein.
Also disclosed herein is a bio-modified composition comprising a
bio-adhesive composition disclosed herein optionally in combination
with asphalt, further optionally wherein the asphalt is recycled
asphalt. Further disclosed herein is a rubber-containing
bio-asphalt composition comprising a bio-adhesive composition as
disclosed herein, in combination with rubber and optionally
comprising an asphalt binder and/or an aggregate other than rubber.
Also disclosed herein is a nanoclay-containing bio-asphalt
comprising a bio-adhesive composition as disclosed herein in
combination with nanoclay and optionally comprising an asphalt
binder and/or an aggregate other than nanoclay.
In one aspect, the present application discloses a method of making
bio-modified asphalt composition comprising contacting components
for an asphalt composition with a bio-adhesion promoter disclosed
herein. In another aspect, the present application discloses a
method of making a bio-modified asphalt composition comprising
contacting components for an asphalt composition with an asphalt
bio-extender as disclosed herein. The present application also
discloses a method of rejuvenating asphalt pavement, comprising
contacting an asphalt composition with a bio-rejuvenator disclosed
herein. In another aspect, the present application discloses a
method of covering a surface with a bio-modified asphalt
composition, comprising contacting the surface with a composition
disclosed herein, optionally wherein the surface is a roof, a road,
a floor, a crack or a joint. In yet another aspect, the present
application discloses a method of sealing a crack or joint in
asphalt pavement comprising applying a bio-modified composition
disclosed herein.
In one aspect, the present application discloses a method of
isolating a bio-adhesive composition from a bio-oil, the method
comprising: (a) providing a bio-oil derived from animal waste; (b)
distilling the bio-oil to remove a light liquid fraction, wherein
the distilling occurs at a vacuum pressure of between about 1 mm Hg
and about 80 mm Hg while heating at a rate of between about
5.degree. C. per hour and about 50.degree. C. to a temperature of
up to 60.degree. C.; (c) isolating a bio-adhesive composition from
the bio-oil under conditions such that the viscosity of the
bio-adhesive composition is not allowed to exceed 1 centipoise (cP)
at 135.degree. C.
In another aspect, the present application discloses a method of
isolating a bio-adhesive composition from a bio-oil, the method
comprising: (a) providing a bio-oil derived from animal waste; (b)
distilling the bio-oil to provide a distilled heavy liquid fraction
and a bio-residue that is not distilled, wherein the distilling
occurs under vacuum pressure while heating at a rate of between
about 5.degree. C. per hour and about 50.degree. C. per hour to (1)
a temperature ranging from 60.degree. C. to 100.degree. C., or (2)
a temperature ranging from 100.degree. C. to 160.degree. C.,
wherein the viscosity of the bio-residue is not allowed to exceed 1
cP at 135.degree. C.; and (c) isolating the bio-adhesive
composition comprising the heavy liquid fraction.
In yet another aspect, the present application discloses a
bio-adhesive composition produced by any of the methods disclosed
herein. In one variation, the present application is directed to a
bio-adhesive composition, comprising a heavy liquid fraction and a
bio-residue, wherein the composition has a viscosity of about 0.5
cP at 135.degree. C. wherein said heavy liquid fraction and
bio-residue is isolated from bio-oil produced from animal waste and
wherein said bio-adhesive composition does not contain a light
liquid fraction. In another variation, the present application is
directed to a bio-adhesive composition, comprising a heavy liquid
fraction having a viscosity of between about 0.1 cP and 0.5 cP at
135.degree. C., optionally, between about 0.2 cP and about 0.5 cP,
wherein said bio-adhesive composition does not contain a light
liquid fraction. In another variation, the present application is
directed to a bio-adhesive composition, comprising a bio-residue
having a viscosity of at least about 0.4 cP, optionally between
about 0.5 cP and 1 cP, at 135.degree. C., wherein said bio-adhesive
composition does not contain a light liquid fraction.
The present application further discloses a bio-adhesion promoter
comprising a bio-adhesive composition disclosed herein. In yet
another aspect, the present application discloses a method of
making bio-modified asphalt composition, comprising contacting
components for an asphalt composition with a bio-adhesion promoter
as disclosed herein.
The present application additionally discloses an asphalt
bio-extender comprising a bio-adhesive composition disclosed herein
and optionally an asphalt binder. In a further aspect, the present
application discloses a method of making a bio-modified asphalt
composition, comprising contacting components for an asphalt
composition with an asphalt bio-extender disclosed herein.
The present application further discloses a bio-rejuvenator
comprising a bio-adhesive composition disclosed herein and
optionally an asphalt binder. In yet another aspect, the present
application discloses a method of rejuvenating asphalt pavement,
comprising contacting an asphalt composition with a bio-rejuvenator
as disclosed herein.
In yet another aspect, the present application discloses a
bio-modified binder comprising a bio-adhesive composition disclosed
herein, and optionally containing asphalt.
In one aspect the present application discloses a rubber-containing
bio-asphalt composition comprising a bio-adhesive composition as
disclosed herein, rubber and optionally an asphalt binder. In
another aspect, the present application discloses
nanoclay-containing bio-asphalt comprising a bio-adhesive
composition as disclosed herein, nanoclay and optionally an asphalt
binder. In one variation, the present application discloses a
method of covering a surface with a bio-modified asphalt
composition, comprising contacting the surface with a composition
disclosed herein. In another variation, the present application
discloses a method of sealing a crack or joint in asphalt pavement
comprising applying a bio-modified composition as disclosed
herein.
These and other objects and aspects of the present inventions will
become apparent to those skilled in the art after a reading of the
following description of the disclosure when considered with the
drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A and FIG. 1B provide schematics summarizing processing and
corresponding products/components in accordance with the presently
disclosed subject matter.
FIG. 2 provides a general schematic outlining of one possible
processing equipment arrangement for the input of raw materials and
the output of the targeted components. Such a process can be
continuous or batch and can be completed by interconnected
equipment or separately configured equipment depending on the
available facilities and identified needs.
FIG. 3 is a bar graph comparing adhesion strength between asphalt
binder and bio-modified binders comprising 5% by weight
bio-binder.
FIG. 4 is a bar graph comparing the m-value, as determined via
Bending Beam Rheometer, of petroleum-based asphalt compared to
bio-modified binder, comprising 2%, 5% or 10% bio-binder by
weight.
FIG. 5A is a graph of reduced frequency vs. dynamic modulus of
RAP-containing asphalt mixtures compared to samples including a
bio-adhesive of the present application.
FIG. 5B is a bar graph of dynamic modulus for each mixture type at
4.degree. C. at a frequency of 10 Hz.
FIG. 5C is a graph of mixture workability test results of
RAP-containing asphalt mixtures compared to samples including a
bio-adhesive of the present application.
FIG. 6A is a graph of the change in viscosity vs. change in
temperature in rubber-containing asphalts comprising asphalt binder
or bio-modified binder.
FIG. 6B is a graph of the change in viscosity vs. change in
temperature in rubber-containing asphalts comprising asphalt binder
or bio-modified binder.
FIG. 7A is a bar graph showing the effect on aging index when
nanoparticle-containing asphalts are combined with bio-modified
binder.
FIG. 7B-1 is a graph showing effect on viscosity when
nanoparticle-containing asphalts are combined with bio-modified
binder. FIG. 7B-2 is an expanded version of FIG. 7B-1 showing the
relationship between temperature in the viscosity range 0.1 to 1.0
Pas.sup.-1.
It will be understood that the drawings are for the purpose of
describing a preferred embodiment of the inventions and are not
intended to limit the inventions thereto.
DETAILED DESCRIPTION
Referring now to FIGS. 1A and 1B, representative process flows in
accordance with the presently disclosed subject matter are
schematically presented, and generally referred to as 100 and 100'.
Animal waste 102 (typically composed of 80% water and 20% solids)
is subjected to thermochemical conversion 104 to produce solid 108,
bio-oil 106 and black water 110. Solid 108 and bio-oil 106 are
subjected to filtration and fractionation 112. Filtration and
fractionation 112 produces bio-char 114 from solid 108 and bio-oil
106. Additionally, filtration and fractionation 112 produces a
light liquid fraction 116, a heavy liquid fraction 118 and a
bio-residue 120 from bio-oil 106. Bio-char 114 can be provided for
bio-soil amendment 124. Light liquid fraction 116, heavy liquid
fraction 118, and bio-residue 120 can be subject to optional
post-processing 122 to produce biofuels 126, bio-rejuvenator 128,
bio-adhesion promoter 130, bio-extender 132, bio-binder 134, and
bio-asphalt 136.
Referring particularly to FIG. 1B, bio-oil 106 can be subjected to
alternative filtration and fractionation 112', described herein
below, to produce light liquid fraction 116' and heavy liquid
fraction plus bio-residue 120'. Heavy liquid fraction plus
bio-residue 120' can be subjected to optional post-processing 122'
to produce bio-binder 134' and bio-asphalt 136', in accordance with
approaches also set forth herein below.
Referring now to FIG. 2, a system for preparing a bio-adhesive
composition in accordance with the presently disclosed subject
matter is referred to generally at 200. System 200 includes
filtration tank 202 wherein a mixture 204 of bio-oil plus solvent
plus bio-char material is loaded. After filtration, removing
biochar (108 in FIG. 1) filtrate 204' is transferred in the
direction of arrow A into vacuum chamber 206 for vacuum
distillation. Vacuum gauge 208 is used to monitor pressures in
vacuum chamber 206. Heater 222 provides heat to vacuum chamber 206.
Filtrate 204 forms fractions: a solvent fraction 210, a Light
Liquid Fraction 212 and Heavy Liquid Fraction/bioresidue 214. In
some embodiments, solvent fraction 210, Light Liquid Fraction 212,
and Heavy Liquid Fraction 214 flow into condenser 215 for further
processing as disclosed herein below. In some embodiments, Heavy
Liquid Fraction/bioresidue 214 is pumped into desiccator 216 via
discharge pump 218, which is controlled by low flow switch 220. A
product P flows out of desiccator 216 for isolation.
Continuing with reference to FIG. 2, in some embodiments, condensed
Light Liquid Fraction 212 and condensed Heavy Liquid Fraction 214
sequentially flow into tank 224, which is in flow communication
with condenser 215 via high level switch 226. Each liquid
condensate is drained from tank 224 via valve 234 for isolation.
Alternatively or in addition, each liquid condensate from tank 224
is pumped into second vacuum chamber 230 for further processing and
interactions as disclosed herein below.
In accordance with the present application and as used herein, the
following terms are defined with the following meanings, unless
explicitly stated otherwise.
"Thermochemical conversion" or "thermochemical liquefaction" refers
to the process converting a liquid slurry of biomass and organic
materials to hydrocarbon oils and byproducts using high pressure
(generally between about 15 MPa and 20 MPa) and temperature
(generally up to 350.degree. C.) in a zero or low oxygen
atmosphere. By-products typically include solids and an aqueous
fraction. The quantity and quality of the end-products are
typically dependent on the reactor system used and feedstock
characteristics.
As used herein, "bio-oil" refers to an oil produced from animal
waste comprising beef, dairy, swine, poultry, sheep manures, or
combinations thereof. The oil is typically an energy-dense crude
oil that is similar to petroleum extracts.
As used herein, "black water" refers to the aqueous side-product
from the production of bio-oil via the thermochemical conversion of
animal waste. Black water contains nutrients, but no pathogens, and
has been identified as a useful fertilizer.
As used herein, "bio-char" refers to the insoluble organic material
isolated from the production and post-processing of the bio-oil, as
described herein. Typically bio-char contains nutrients, including
but not limited to carbon, metals, sand solid minerals comprising,
amongst others, elements such as nitrogen, phosphorus, potassium,
and calcium.
As used herein "Light Liquid Fraction" refers to liquid compounds
within bio-oil that have relatively low boiling point at 3 mm
mercury (Hg), generally up to 60.degree. C. The Light Liquid
Fraction typically contains olefin compounds and is usually an
odorous fraction. The molecules in the fraction include, but are
not limited to hexadecanamide, tetradecanal o-methyloxime, and
octadecanoic acid. The Light Liquid Fraction has applications as
sources of energy, including but not limited to transportation
fuel, heating fuel, and use in creating electricity, optionally in
conjunction with a methane digester.
As used herein "Heavy Liquid Fraction" refers to liquid compounds
within bio-oil that have mid-range boiling points at 3 mm Hg,
typically over 60.degree. C., generally from 60.degree. C. to
100.degree. C. and from 100.degree. C. to 160.degree. C. These
compounds are liquid at room temperature and have adhesion
characteristics to certain surfaces (substrates). They have
apparent dynamic viscosity of up to about 0.5 cP at 135.degree. C.,
generally between about 0.1 cP and about 0.5 cP. This fraction can
have a slight sulfurous odor. The Heavy Liquid Fraction can be
isolated as a series of sub-fractions, for example, a fraction
containing hydrocarbons with a high concentration of amide groups,
for example at least about 5% or at least about 10%, or at least
about 15% by weight amide containing compounds. Alternately, one
Heavy Liquid Fraction contains between about 10% and about 20%
amide containing compounds. Alternately a Heavy Liquid Fraction
contains a low concentration of amide groups, for example no more
than about 10% amide-containing compounds or no more than about 5%
amide-containing compounds or nor more than about 2% amide
containing compounds. The isolation of these Heavy Liquid
sub-Fractions depends on the isolation methods used, as disclosed
herein.
As used herein, "bio-residue" refers to a dark brown to black
sticky material that is solid at room temperature with penetration
grade between (25-60) at 25.degree. C. Typically the bio-residue is
non-odorous at room temperature and has a slight sulfurous odor at
elevated temperatures. Generally bio-residue contains compounds
that are highly polar, have low aromaticity, including some
olefinic compounds, and those with a lower molecular weight.
Generally, the viscosity of the bio-residue is targeted to be less
than 5.0 cP at 135.degree. C. In one embodiment, the bio-residue
has a viscosity of at least about 0.1 cP, at least about 0.05 cP at
135.degree. C., or at least about 0.1 cP; alternately the
bio-residue has a viscosity of at least about 0.2 cP, at least
about 0.3 cP, or at least about 0.4 cP at 135.degree. C. In one
variation, the bio-residue has a viscosity of at least 0.5 cP at
135.degree. C. In another embodiment, at 135.degree. C. the
bio-residue has a viscosity of at least about 0.6 cP, at least
about 0.7 cP, at least about 0.8 cP, at least about 0.9 cP, at
least about 1 cP, or at least about 1.5 cP. In yet another
embodiment, the bio-residue at 135.degree. C. has a viscosity of no
more than about 2 cP, no more than about 3 cP, no more than about 4
cP, or no more than about 5 cP. In one alternative, the bio-residue
has a viscosity of between about 0.1 cP and about 3 cP at
135.degree. C. In another alternative, the bio-residue has a
viscosity of between about 0.3 cP and about 2 cP or between about
0.5 and about 1 cP at 135.degree. C.
As used herein, "bio-adhesive" refers to a group of compounds that
can be isolated from bio-oil prepared from animal waste; typically
bio-adhesives have a viscosity between about 0.01 cP and about 5 cP
at 135.degree. C. In one embodiment, the source of the animal waste
is cattle, swine, poultry, sheep or combinations thereof. In
another embodiment, the animal waste comprises beef manure, dairy
manure, swine manure, sheep manure, poultry manure or combinations
thereof. In yet another embodiment, the animal waste comprises
poultry manure. In another embodiment, the animal waste comprises
beef or dairy manure. In yet another embodiment, the animal waste
comprises sheep manure. In another embodiment, the animal waste
comprises swine manure.
In one embodiment, the minimal percentage of animal waste that is
solid manure waste, as opposed to liquid waste, straw, grass etc.,
is at least 2.5% by weight or alternately about 5% by weight. In
another embodiment, the percentage of solid manure waste is at
least about 10% by weight, at least about 15%, at least about 20%,
at least about 25% or at least about 30% by weight. The liquid
component of animal waste can be removed or alternately its amount
reduced by a variety of methods, including but not limited to,
filtration, centrifugation, condensation, gravimetry and other
methods familiar to those of skill in the art for separating solids
and liquids. In one embodiment, the animal waste is processed by
thermochemical liquefaction. In another embodiment, animal waste is
processed by chemical reactions in presence of a catalyst,
including, but not limited to gasification, anaerobic digestion or
fast pyrolysis. Alternately, the animal waste is processed though a
digester leading to side products, that can be used as a feedstock
for the production of bio-oil, for example a centroid from a
methane digester and/or glycerol from bio-diesel production.
Generally, the viscosity of the bio-adhesive is targeted to be less
than 5.0 cP at 135.degree. C. In one embodiment, the bio-adhesive
has a viscosity of about 0.01 cP, about 0.05 cP at 135.degree. C.,
or about 0.1 cP; alternately the bio-adhesive has a viscosity of
about 0.2 cP, about 0.3 cP, or about 0.4 cP at 135.degree. C. In
one variation, the bio-adhesive has a viscosity of 0.5 cP at
135.degree. C. In another embodiment, at 135.degree. C. the
bio-adhesive has a viscosity of about 0.6 cP, about 0.7 cP, about
0.8 cP, about 0.9 cP or about 1 cP. In yet another embodiment, the
bio-adhesive at 135.degree. C. has a viscosity of about 2 cP or
about 3 cP or about 4 cP or about 5 cP. In one alternative, the
bio-adhesive has a viscosity of between about 0.01 cP and about 3
cP at 135.degree. C. In another alternative, the bio-adhesive has a
viscosity of between about 0.01 cP and about 1 cP, between about
0.01 cP and about 0.5 cP or between about 0.1 and 0.3 cP at
135.degree. C. Alternately, the bio-adhesive has a viscosity of up
to about 1 cP or up to about 0.5 cP or up to about 0.3 cP at
135.degree. C.
As used herein "bio-adhesion promoter" refers to one industrial
application of a bio-adhesive prepared according to the methods of
the present application, in which the bio-adhesion promoter
improves the interaction between asphalt and the aggregates
comprising asphalt concrete as disclosed herein. Typically, the
bio-adhesion promoter is isolated as part of the Heavy Liquid
Fraction. Usually, the bio-adhesion promoter is comprised of at
least about 5% by weight amide containing compounds. In one
embodiment, the bio-adhesion promoter is comprised of at least
about 10% amide containing compounds or at least about 15% amide
containing compounds. In another embodiment, the bio-adhesion
promoter is comprised of between about 5% and about 20% amide
containing compounds; alternately, the bio-adhesion promoter is
comprised of between about 10 and about 15% amide containing
compounds. Generally, the bio-adhesive component with the targeted
viscosities and amide concentrations are combined with bitumen to
yield an industrially useful bio-adhesion promoter. Usually the
bio-adhesive component is combined at about 1% to about 10% by
weight with bitumen, for example the bio-adhesive component is
combined at about 1% or about 2% or about 3% or about 4% or about
5% or about 6% or about 7% or about 8% or about 9% or about 10% by
weight with bitumen.
Typically, a successful bio-adhesion promoter of the present
application has a viscosity between about 0.01 cP and about 3 cP at
135.degree. C. Alternately, the bio-adhesion promoter has a
viscosity of about 0.01 cP, about 0.05 cP at 135.degree. C., or
about 0.1 cP; alternately the bio-adhesion promoter has a viscosity
of about 0.2 cP, about 0.3 cP, about 0.4 cP or 0.5 cP at
135.degree. C. In another embodiment, at 135.degree. C. the
bio-adhesion promoter has a viscosity of about 0.6 cP, about 0.7
cP, about 0.8 cP, about 0.9 cP or about 1 cP. In yet another
embodiment, the bio-adhesion promoter at 135.degree. C. has a
viscosity of about 2 cP or about 2.5 cP. In one alternative, the
bio-adhesion promoter has a viscosity of between about 0.05 cP and
about 2 cP at 135.degree. C. In another alternative, the
bio-adhesion promoter has a viscosity of between about 0.1 cP and
about 1.5 cP or between about 0.1 cP and about 0.5 cP at
135.degree. C. Alternately, the bio-adhesion promoter has a
viscosity of up to about 1 cP or up to about 0.5 cP. Bio-adhesion
promoters having the targeted viscosity and/or amide concentration
can be prepared according to the methods of the present
application.
As used herein "asphalt bio-extender" refers to one industrial
application of a bio-adhesive prepared according to the methods of
the present application, in which the asphalt bio-extender enables
the recycling of asphalt waste, such as RAP or RAS, as well as
incorporating natural asphalt sources, including but not limited
to, rock asphalt, tar sands, Gilsonite, and Trinidad Lake Asphalt.
Asphalt bio-extenders generally enable a larger amount of asphalt
waste material to be used in a performance grade asphalt mix,
yielding a product having targeted mechanical and physical
properties. Typically, the asphalt bio-extender is isolated as part
of the Heavy Liquid Fraction.
Typically, a successful asphalt bio-extender has a viscosity
between about 0.01 cP and about 1 cP at 135.degree. C. Alternately,
the asphalt bio-extender has a viscosity of about 0.01 cP, about
0.05 cP at 135.degree. C., or about 0.1 cP; alternately the asphalt
bio-extender has a viscosity of about 0.2 cP, about 0.3 cP, about
0.4 cP or 0.5 cP at 135.degree. C. In one embodiment, at
135.degree. C. the asphalt bio-extender has a viscosity of about
0.6 cP, about 0.7 cP, about 0.8 cP, about 0.9 cP or about 1 cP. In
yet another embodiment, the asphalt bio-extender has a viscosity of
between about 0.01 cP and about 0.5 cP at 135.degree. C. In another
alternative, the asphalt bio-extender has a viscosity of between
about 0.1 cP and about 0.5 cP or between about 0.2 cP and about 0.5
cP at 135.degree. C. Alternately, the asphalt bio-extender has a
viscosity of up to about 1 cP or up to about 0.5 cP. Asphalt
bio-extenders having the targeted viscosity can be prepared
according to the methods of the present application.
The asphalt bio-extender disclosed herein is generally combined
with asphalt in the refinery, at the blending terminal or some
combination thereof. It can also be introduced to reclaimed asphalt
pavement and recycled asphalt shingles in an amount sufficient to
eliminate the adverse stiffening effects of the
reclaimed/recycled/asphalt from pavement and/or tear-off and/or
manufactured scrap roofing shingles. The bio-asphalt extender is
typically present in an amount of about 5% to about 75% by weight,
or in an amount from about 15% to about 50% by weight, or in an
amount from about 10% to about 40% by weight, of the total liquid
asphalt needed for performance grade asphalt mix. In turn, the
amount of liquid asphalt is from about 25% to about 95% of the
total weight of the final performance graded asphalt mix. The
amount asphalt waste material is from about 2% to about 45% of the
total weight of the performance graded asphalt mix; or from about
8% to about 35% of the total weight of the performance graded
asphalt mix; or from about 10% to about 25% of the total weight of
the performance graded asphalt mix. The amount of aggregate
comprises from about 50% to about 95% of the total weight of the
performance grade asphalt mix, as typically identified in AASHTO
standards. The mixing temperature at which asphalt bio-extender is
blended with the asphalt, reclaimed/recycled asphalt, and aggregate
is generally from about 80.degree. F. to about 300.degree. F.
As used herein "asphalt bio-rejuvenator" refers to one industrial
application of the bio-adhesive prepared according to the methods
of the present application, in which the asphalt bio-rejuvenator is
used to for one or more of the following: stops and/or reverses
shrinking, inhibits pitting and/or raveling, and reduces air and/or
water permeability. Typically, bio-rejuvenator inhibits processes
leading to pavement degradation. Usually, the asphalt
bio-rejuvenator is isolated as part of the Heavy Liquid
Fraction.
Typically, a successful asphalt bio-rejuvenator has a viscosity
between about 0.01 cP and about 3 cP at 135.degree. C. Alternately,
the bio-rejuvenator has a viscosity of about 0.01 cP, about 0.05 cP
at 135.degree. C., or about 0.1 cP; alternately the bio-rejuvenator
has a viscosity of about 0.2 cP, about 0.3 cP, about 0.4 cP or 0.5
cP at 135.degree. C. In another embodiment, at 135.degree. C. the
bio-rejuvenator has a viscosity of about 0.6 cP, about 0.7 cP,
about 0.8 cP, about 0.9 cP or about 1 cP. In yet another
embodiment, the bio-rejuvenator at 135.degree. C. has a viscosity
of about 2 cP or about 2.5 cP. In one alternative, the
bio-rejuvenator has a viscosity of between about 0.01 cP and about
3 cP at 135.degree. C. In another alternative, the bio-rejuvenator
has a viscosity of between about 0.1 cP and about 0.5 cP or between
about 0.2 cP and 0.5 cP at 135.degree. C. Alternately, the
bio-rejuvenator promoter has a viscosity of up to about 1 cP or up
to about 0.5 cP at 135.degree. C.
Asphalt bio-rejuvenator having the targeted viscosity can be
prepared according to the methods of the present application.
As used herein "bitumen" or "asphalt" is the sticky, black and
highly viscous liquid or semi-solid present in most crude petroleum
and in some natural deposits. Asphalt is used in asphalt binders,
adhesion promoters, asphalt rejuvenators, asphalt extenders, as
well as asphalt mixtures with nanoclay or rubber. In addition,
asphalt can also be used in roofing, soil stabilization, crack and
joint sealing and carpeting as a hot-melt adhesive and to enhance
U.V. protection in case of roofing. In such specialty products
asphalt has been shown to be an effective base material.
As used herein "bio-asphalt" refers to an industrial application of
the bio-adhesive prepared according to the methods of the present
application, in which the bio-adhesive is used as a stand-alone
bio-degradable product having some of the properties of
petroleum-based asphalt, such as viscosity and stickiness.
Typically the uses of bio-asphalt encompass known uses of
petroleum-based asphalt, including but not limited to roofing, soil
stabilization, crack and joint sealing, flooring adhesives and
roofing.
Typically the bio-adhesive employed as a bio-asphalt (referred to
at 136 in FIG. 1A) is isolated from the bio-residue (referred to at
120 in FIG. 1A), as represented in FIG. 1A. Generally in this
example, a successful bio-asphalt has a viscosity between about 0.4
cP and about 5 cP at 135.degree. C. Alternately, the bio-asphalt at
135.degree. C. has a viscosity of about 0.5 cP, about 1 cP, about
1.5 cP, about 2 cP or about 2.5 cP or about 3 cP or about 3.5 cP or
about 4 cP or about 4.5 cP. In one alternative, the bio-asphalt has
a viscosity of between about 0.5 cP and about 1 cP at 135.degree.
C. In another alternative, the bio-asphalt has a viscosity of
between about 0.4 cP and about 2.5 cP or about 0.5 cP and about 1.5
cP at 135.degree. C. Alternately, the bio-asphalt has a viscosity
of up to about 2.5 cP or up to about 1 cP or up to about 0.5 cP at
135.degree. C. A bio-asphalt having the targeted viscosity can be
prepared according to the methods of the present application.
Alternately, the bio-adhesive employed as a bio-asphalt (referred
to at 136' in FIG. 1B) is isolated from un-separated combination of
bio-residue and Heavy Liquid Fraction (referred to at 120' in FIG.
1B), as represented in FIG. 1B. Typically in this example, a
successful bio-asphalt has a viscosity between about 0.1 cP and
about 5 cP at 135.degree. C. Alternately, the bio-asphalt has a
viscosity of about 0.2 cP, about 0.3 cP, about 0.4 cP or 0.5 cP at
135.degree. C. In another embodiment, at 135.degree. C. the
bio-asphalt has a viscosity of about 0.6 cP, about 0.7 cP, about
0.8 cP, or about 0.9 cP. Alternately, the bio-asphalt at
135.degree. C. has a viscosity of about 1 cP, about 1.5 cP, about 2
cP or about 2.5 cP or about 3 cP or about 3.5 cP or about 4 cP or
about 4.5 cP. In one alternative, the bio-asphalt has a viscosity
of between about 0.1 cP and about 1 cP at 135.degree. C. In another
alternative, the bio-asphalt has a viscosity of between about 0.5
cP and about 1 cP at 135.degree. C. In yet another alternative, the
bio-asphalt has a viscosity of between about 0.4 cP and about 2.5
cP or about 0.5 cP and about 1.5 cP at 135.degree. C. Alternately,
the bio-asphalt has a viscosity of up to about 2.5 cP, up to about
1 cP or up to about 0.5 cP. A bio-asphalt having the targeted
viscosity can be prepared according to the methods of the present
application.
In one variation, the bio-residue of the present application is
used without the addition of any petroleum-based adhesive,
generally as a bio-asphalt. Alternately, bio-residue of the present
application optionally can be combined with modifiers selected from
the group including but not limited to nanoclay and rubber. In one
variation, the bio-residue is blended with nanoclay to yield a
nanoclay-containing bio-asphalt, which is typically a brittle
material used in molding vases, low cost containers, animal feed
containers, sport goods, etc. In another variation the bio-residue
is blended with rubber to yield a rubber-containing bio-asphalt,
which is typically a flexible material with higher strength length.
Rubber-containing bio-asphalt has applications in sealing cracks
and joints, which generally requires high elasticity.
As used herein "asphalt concrete" refers to a composite containing
asphalt and aggregate, prepared using standard methods, including
warm mix, semi-cold mix, cold mix, and hot mix asphalt
technologies.
The term "aggregate" refers to materials such as stone aggregate,
crushed stone, tar sands, slag, natural sand, stone sand, stone
dust, soil, or similar materials. Aggregate can optionally further
contain and rubber-based material, including but not limited to
ground rubber, crumb rubber, virgin rubber, or similar
materials.
The phrase "asphalt binder" or "petroleum binder," as used herein
is generally consistent with the meaning provided by AASHTO M320 or
ASTM D-6373. The asphalt binder material may be derived from any
asphalt source, such as natural asphalt, rock asphalt, produced
from tar sands, or petroleum-based asphalt. The asphalt binder may
be selected from those currently graded by AASHTO M320 and ASTM
D-6373, including Performance Graded Asphalt Binders.
As used herein, a "binder mixture" may contain a petroleum-based
asphalt binder, a polymer-based asphalt binder additive, or
combinations thereof. Asphalt binders may further include a blend
of various asphalts not meeting any specific grade definition,
including air-blown asphalt, vacuum-distilled asphalt,
steam-distilled asphalt, cutback asphalt or roofing asphalt.
Alternatively, synthetic binders, such as gilsonite (natural or
synthetic) can be used alone or mixed with petroleum asphalt as a
binder. When asphalt binder mixtures contain a bio-adhesive
prepared according to the methods of the present application, such
mixtures are typically referred to as "bio-modified asphalt
mixtures" (BMAM).
As used herein "bio-binder" refers to an industrial application of
the bio-adhesive prepared according to the methods of the present
application, in which the bio-adhesive has a minimum viscosity of
about 0.3 cP at 135.degree. C., usually a measured viscosity of
about 0.5 cP at 135.degree. C. Typically the bio-residue (referred
to at 120 in FIG. 1A) from bio-oil (referred to at 106 in FIG. 1A)
is employed as a bio-binder ((referred to at 134 in FIG. 1A)), in
which the viscosity is at least about 0.5 cP at 135.degree. C.
Alternately, according to another variation in the current
application, the Heavy Liquid Fraction and the bio-residue
(referred to at 120' in FIG. 1B) are not fully separated in
post-processing and the mixture of components is employed as a
bio-binder ((referred to at 134' in FIG. 1B)), in which the
viscosity is between about 0.1 cP and about 5 cP at 135.degree. C.
In another variation, the viscosity is up to about 2.5 cP or up to
about 1 cP or up to about 0.5 cP.
Typically the bio-adhesive employed as a bio-binder (referred to at
134 in FIG. 1A) is isolated from the bio-residue (referred to at
120 in FIG. 1A), as represented in FIG. 1A. Generally in this
example, a successful bio-binder has a viscosity between about 0.5
cP and about 5 cP at 135.degree. C. Alternately, the bio-binder at
135.degree. C. has a viscosity of about 1 cP, about 1.5 cP, about 2
cP or about 2.5 cP or about 3 cP or about 3.5 cP or about 4 cP or
about 4.5 cP. In one alternative, the bio-binder has a viscosity of
between about 0.5 cP and about 1 cP at 135.degree. C. In another
alternative, the bio-binder has a viscosity of between about 0.4 cP
and about 2.5 cP or about 0.5 cP and about 1.5 cP at 135.degree. C.
In yet another alternative, the bio-binder has a viscosity of
between about 0.5 cP and about 0.75 cP at 135.degree. C.
Alternately, the bio-binder has a viscosity of up to about 2.5 cP,
up to about 1 cP or up to about 0.5 cP at 135.degree. C. A
bio-binder having the targeted viscosity can be prepared according
to the methods of the present application.
Alternately, the bio-adhesive employed as a bio-binder (referred to
at 134' in FIG. 1A) is isolated from unseparated combination of
bio-residue and Heavy Liquid Fraction (referred to at 120' in FIG.
1A), as represented in FIG. 1B. Typically in this example, a
successful bio-binder has a viscosity between about 0.1 cP and
about 5 cP at 135.degree. C. Alternately, the bio-binder has a
viscosity of about 0.2 cP, about 0.3 cP, about 0.4 cP or 0.5 cP at
135.degree. C. In another embodiment, at 135.degree. C. the
bio-binder has a viscosity of about 0.6 cP, about 0.7 cP, about 0.8
cP, or about 0.9 cP. Alternately, the bio-binder at 135.degree. C.
has a viscosity of about 1 cP, about 1.5 cP, about 2 cP or about
2.5 cP or about 3 cP or about 3.5 cP or about 4 cP or about 4.5 cP.
In one alternative, the bio-binder has a viscosity of between about
0.1 cP and about 1 cP at 135.degree. C. In another alternative, the
bio-binder has a viscosity of between about 0.3 cP and about 0.8 cP
at 135.degree. C. Alternately, the bio-binder has a viscosity of up
to about 2.5 cP, up to about 0.8 cP or up to about 0.5 cP. A
bio-binder having the targeted viscosity can be prepared according
to the methods of the present application.
As used herein, "bio-modified binder" (BMB) refers to an asphalt
binder combined with the bio-binder of the present application. In
one embodiment the BMB comprises at least about 2% by weight
bio-binder. In another embodiment the bio-binder is combined with
asphalt binder up to about 50% by weight of the final BMB,
alternately at between about 2% and about 50% by weight of the
final BMB. In one variation, the BMB comprises between about 5% and
about 45%, between about 10% and about 40%, between about 15% and
about 35%, or between about 20% and about 30% bio-binder. In one
variation, the BMB comprises at least about 2% or at least about 5%
or at least about 10% or at least about 15% or at least about 20%
or at least about 25% or at least about 30% or at least about 35%
or at least about 40% or at least about 45% or at least about 50%
bio-binder.
Asphalt binders, prior to combination with bio-binder, can be
characterized by their temperature performance range, which is
usually 86.degree. C. Familiar to those of skill in the art, PG
rating refers to Super Pave (Superior Performing Pavements)
Performance Graded (PG) binder specifications as developed in the
United States through research funded by the Association of
American Highway and Transportation Officials (AASHTO M320). PG
ratings, e.g. PG 64-22, are identified by a first number, (64)
which is equivalent to the maximum 7 day temperature (in .degree.
C.) for which the binder is tested; the second number (-22) is the
minimum temperature (in .degree. C.) at which cracking caused by
low temperatures is not observed. Typically, commercial asphalt
binders have a PG rating of PG 64-22, PG 52-28, or PG 52-34, etc.
Combining commercial and non-commercial asphalt binders with the
bio-binder of the present application leads to a bio-modified
binder, which is eco-friendly and has a broader PG range and/or
allows asphalt binders having a broader temperature performance
range to be industrially useful. For example, a BMB containing PG
64-28 (with 92.degree. C. useful temperature interval) can be
prepared by blending BMB with PG 64-22 (with 86.degree. C. useful
temperature interval).
As used herein, "RAP" refers to Reclaimed Asphalt Pavements, the
term typically given to removed and reprocessed pavement materials
containing asphalt and aggregates. RAP generally contains 3%-7%
asphalt by weight. RAP is usually used in surface asphalt mixtures
at no more than 20%, due to limitations on the resulting asphalt
quality. Without being bound by theory, it is believed that the
aged binder in RAP is one of the factors leading to increased
mixture stiffness. Addition of BMB can facilitate blending of the
aged binder in RAP and virgin binder allowing for introduction of
about 20%-30% higher RAP into the mixture, so for example the
amount of RAP used in surface asphalt mixtures comprising
bio-binder can range from about 20% up to about 50%. The percent of
RAP in the mixture can be at least about 25%, at least about 30%,
at least about 35%, at least about 40%, at least about 45% or at
least about 50% of the overall surface asphalt mixture.
As used herein "RAS" refers to recycled asphalt shingles. RAS are
generally composed of 30%-35% asphalt cement by weight. RAS is
usually used in surface asphalt mixtures at no more than 5%, due to
limitations on the resulting asphalt quality. Without being bound
by theory, it is believe that the aged binder in RAS is one of the
factors leading to increased mixture stiffness, analogous to aged
RAP. Addition of BMB can facilitate blending of the aged binder in
RAS and virgin binder allowing for introduction of about 10%-15%
higher RAS into the mixture, so for example the amount of RAS used
in surface asphalt mixtures comprising bio-binder can range from
about 5% up to about 20%. The percent of RAS in the mixture can be
at least about 10%, at least about 15%, or at least about 20% of
the overall surface asphalt mixture.
"Rubber" as used herein generally refers to recycled rubber, but
can also include proportions of virgin rubber. A typical, but not
exclusive, source of recycled rubber is used tires.
The present application generally discloses a method of vacuum
distillation that can separate industrially useful fractions of
bio-oil while controlling the viscosity of the resulting
commercially relevant residue.
As disclosed herein, and referring to FIGS. 1A and 1B, process
flows for converting animal waste are referred to generally as 100
and 100'. In processes 100 and 100' animal waste 102 can be
converted to bio-oil 106 using methods known to those of skill in
the art, including, but not limited to thermochemical liquefaction
and catalyzed chemical modification, referred to at 104 in FIGS. 1A
and 1B. The resulting bio-oil 106 can then be processed according
to processes 100 and 100' to produce a variety of industrially
useful components, including but not limited to: bio-char 114, a
light liquid component 116, a heavy liquid component 118, and a
bio-adhesive residue 120. In one variation, the processing of
bio-oil 106 comprises adding a solvent, such as acetone or an
acetone/toluene mix to the product of the thermochemical
liquefaction, a mixture of bio-char+bio-oil and transferring to
mixture to a filtration device (all of which are referred to
schematically at 112 and 112' in FIGS. 1A and 1B), which separates
out the insoluble bio-char 114 and 114'. The bio-oil 106 in
solution is transferred to a vacuum distillation apparatus
(referred to schematically at 112 and 112' in FIGS. 1A and 1B and
at 206 in FIG. 2). The apparatus is set to a pressure of between
about 1 mm Hg and about 80 mm Hg. Alternately the pressure of the
apparatus can be set to at least about 1 mm Hg, at least about 2 mm
Hg, at least about 3 mm Hg, at least about 4 mm Hg, at least about
5 mm Hg, at least about 6 mm Hg, at least about 7 mm Hg, at least
about 8 mm Hg, at least about 9 mm Hg or at least about 10 mm Hg.
In another variation the pressure of the apparatus can be set to no
more than about 20 mm Hg, no more than about 30 mm Hg, no more than
about 40 mm Hg, no more than about 50 mm Hg, no more than about 60
mm Hg, no more than about 70 mm Hg or no more than about 80 mm Hg.
In another variation, the apparatus is heated at a rate of between
about 5.degree. C. per hour and about 50.degree. C. per hour to a
final temperature of between about 130.degree. C. and about
250.degree. C. In one variation, the heating rate is between about
10.degree. C. per hour and about 45.degree. C. per hour,
alternately between about 15.degree. C. per hour and about
40.degree. C. per hour, or between about 20.degree. C. per hour and
about 35.degree. C. per hour, or between about 25.degree. C. per
hour and about 30.degree. C. per hour. In another variation, the
heating rate is no more than about 5.degree. C. per hour, no more
than about 10.degree. C. per hour, no more than about 15.degree. C.
per hour, no more than about 20.degree. C. per hour, no more than
about 25.degree. C. per hour, no more than about 30.degree. C. per
hour, no more than about 35.degree. C. per hour, no more than about
40.degree. C. per hour, no more than about 45.degree. C. per hour
or no more than about 50.degree. C. per hour. In one variation, the
temperature is not raised above about 130.degree. C., or above
about 140.degree. C., or above about 150.degree. C., or above about
160.degree. C., or above about 170.degree. C., or above about
180.degree. C., or above about 190.degree. C., or above about
200.degree. C., or above about 210.degree. C., or above about
220.degree. C., or above about 230.degree. C., or above about
240.degree. C., or above about 250.degree. C. In one embodiment,
the pressure range is between about 1 mm Hg and about 5 mm Hg and
the temperature heating rate is no more than about 30.degree. C.
per hour to a final temperature of no more than about 160.degree.
C., alternately to a final temperature of no more than about
100.degree. C. In another embodiment, the pressure range is between
about 2 mm Hg and about 10 mm Hg and the heating rate is no more
than about 15.degree. C. per hour to a final temperature of not
more than about 170.degree. C., alternately to a final temperature
of no more than about 130.degree. C. In another embodiment, the
pressure range is between about 5 mm Hg and about 15 mm Hg and the
heating rate is no more than about 10.degree. C. per hour to a
final temperature of not more than about 180.degree. C.,
alternately to a final temperature of not more than about
150.degree. C. In another embodiment, the pressure range is between
about 10 mm Hg and about 30 mm Hg and the heating rate is no more
than about 10.degree. C. per hour to a final temperature of not
more than about 170.degree. C., alternately to a final temperature
of not more than about 160.degree. C. In another embodiment, the
pressure range is between about 30 mm Hg and about 50 mm Hg and the
heating rate is no more than about 10.degree. C. per hour to a
final temperature of not more than about 160.degree. C. In another
embodiment, the pressure range is between about 50 mm Hg and about
70 mm Hg and the heating rate is no more than about 10.degree. C.
per hour to a final temperature of not more than about 180.degree.
C. In one variation of any of the disclosed embodiments, the
heating rate is no more than about 5.degree. C. per hour.
Typically, the viscosity of the bio-adhesive composition remaining
in the distillation pot is monitored on a regular basis. For
example, the viscosity of the bio-adhesive composition can be
monitored every 30 minutes, every 20 minutes, every 10 minutes or
every 5 minutes. Alternately, the viscosity of the bio-adhesive
composition can be measured continuously. Using methods known to
those of skill in the art, viscosity can be determined by removing
small samples from the distillation pot, or alternately, the
distillation pot can be adapted to measure viscosity in situ, e.g.
the viscosity can be measured by determining the torque necessary
to stir the pot liquor.
In one aspect, the present application discloses a method of
isolating a bio-adhesive composition from a bio-oil, the method
comprising: (a) providing a bio-oil derived from animal waste; (b)
distilling the bio-oil to remove a light liquid fraction, wherein
the distilling occurs at a vacuum pressure of between about 1 mm Hg
and about 80 mm Hg while heating to a temperature of up to about
60.degree. C., optionally wherein the rate of the heating is
between about 5.degree. C. per hour and about 50.degree. C. per
hour; and (c) isolating a bio-adhesive composition from the bio-oil
under conditions such that the viscosity of the bio-adhesive
composition is not allowed to exceed about 1 centipoise (cP) at
135.degree. C., optionally wherein the viscosity of the
bio-adhesive composition is not allowed to exceed about 0.5 cP at
135.degree. C. In one variation, the bio-adhesive composition
comprises a heavy liquid fraction and a bio-residue. In another
variation, the method further comprises using the bio-adhesive
composition as a component of a composition selected from the group
consisting of a bio-adhesion promoter, an asphalt bio-extender, a
bio-rejuvenator, a biomodified binder, and a bio-asphalt, wherein
the bio-asphalt is optionally a rubber-containing bio-asphalt or a
nanoclay-containing bio-asphalt.
In another aspect, the present application discloses a method of
isolating a bio-adhesive composition from a bio-oil, the method
comprising: (a) providing a bio-oil derived from animal waste; (b)
distilling the bio-oil to provide a distilled heavy liquid fraction
and a bio-residue that is not distilled, wherein the distilling
occurs under vacuum pressure, optionally of between about 1 mm Hg
and about 80 mm Hg, while heating to (1) a temperature ranging from
about 60.degree. C. to about 100.degree. C., or (2) a temperature
ranging from about 100.degree. C. to about 160.degree. C., wherein
the viscosity of the bio-residue is not allowed to exceed about 1
cP at 135.degree. C., optionally wherein the viscosity of the
bio-residue is not allowed to exceed about 0.5 cP at 135.degree. C.
and further optionally wherein the rate of the heating is between
about 5.degree. C. per hour and about 50.degree. C. per hour; and
(c) isolating the bio-adhesive composition comprising the heavy
liquid fraction.
In one variation of any disclosed aspect or embodiment, the method
further comprises isolating a bio-adhesive composition comprising
the bio-residue. In embodiment, the animal waste comprises beef
manure, dairy manure, swine manure, sheep manure, poultry manure or
combinations thereof. In another variation, the temperature ranges
from about 60.degree. C. to about 100.degree. C. and the
bio-adhesive composition comprises a heavy liquid fraction
comprising at least about 5% by weight of amide-containing
compounds, optionally wherein the composition comprises a heavy
liquid fraction comprising between about 10% and about 20% by
weight of amide-containing compounds. In another variation, the
temperature ranges from 100.degree. C. to 160.degree. C. and the
bio-adhesive composition comprises a heavy liquid fraction
comprising up to about 5% by weight of amide-containing compounds,
optionally wherein the composition comprises a heavy liquid
fraction comprising between about 1% and about 5% by weight of
amide-containing compounds. In one embodiment, the method further
comprises distilling the bio-oil to remove a light liquid fraction,
wherein the distilling occurs at vacuum pressure between about 1 mm
Hg and about 80 mm Hg while heating a temperature of up to
60.degree. C., optionally wherein the rate of the heating is
between about 5.degree. C. per hour and about 50.degree. C. per
hour. In another embodiment, the animal waste comprises swine
manure and the vacuum pressure is between about 1 mm and about 40
mm Hg, optionally wherein the vacuum pressure is between about 1 mm
and about 10 mm Hg. In yet another embodiment, the bio-oil is
treated with a solvent to provide a bio-char, optionally, wherein
the bio-char is isolated by filtration. In one variation, the
method further comprises using the bio-adhesive composition as a
component of a composition selected from the group consisting of a
bio-adhesion promoter, an asphalt bio-extender, and a
bio-rejuvenator. In another variation, the method further comprises
using the bio-adhesive composition comprising the bio-residue as a
component of a composition selected from the group consisting of a
bio-modified binder and a bio-asphalt, wherein the bio-asphalt is
optionally a rubber-containing bio-asphalt or a nanoclay-containing
bio-asphalt.
The present application discloses a bio-adhesive composition
produced by any of the methods disclosed herein.
In one aspect, the present application discloses a bio-adhesive
composition comprising a heavy liquid fraction and a bio-residue,
wherein the composition has a viscosity of at least about 0.5 cP at
135.degree. C., optionally between about 0.5 cP and about 1 cP at
135.degree. C. wherein said heavy liquid fraction and bio-residue
are isolated from bio-oil produced from animal waste and wherein
said bio-adhesive composition does not contain a light liquid
fraction.
In another aspect, the present application discloses a bio-adhesive
composition comprising a heavy liquid fraction having a viscosity
of between about 0.1 cP and 0.5 cP at 135.degree. C., optionally,
between about 0.2 cP and about 0.5 cP, wherein said bio-adhesive
composition does not contain a light liquid fraction and wherein
said heavy liquid fraction is isolated from bio-oil produced from
animal waste.
In one embodiment, the present application discloses a bio-adhesive
composition comprising (a) a heavy liquid fraction comprising at
least about 5% by weight of amide-containing compounds, optionally
containing about 10% to about 20% by weight of amide-containing
compounds, or (b) a heavy liquid fraction comprising up to about 5%
by weight of amide-containing compounds, optionally about 1% to
about 5% by weight of amide-containing compounds, wherein said
bio-adhesive composition does not contain a light liquid
fraction.
In another aspect, the present application discloses a bio-adhesive
composition comprising a bio-residue having a viscosity of at least
about 0.4 cP, optionally between about 0.5 cP and 1 cP, at
135.degree. C., wherein said bio-adhesive composition does not
contain a light liquid fraction and wherein said bio-residue is
isolated from bio-oil produced from animal waste.
In yet another aspect, the present application discloses a
bio-adhesion promoter comprising a bio-adhesive composition of the
present application, optionally wherein the bio-adhesive
composition comprises at least about 5% by weight amide-containing
compounds. The present application also discloses a method of
making bio-modified asphalt composition comprising contacting
components for an asphalt composition with a bio-adhesion promoter
disclosed herein.
In yet another aspect, the present application discloses an asphalt
bio-extender comprising a bio-adhesive composition disclosed
herein, and optionally an asphalt binder. In another aspect, the
present application discloses a method of making a bio-modified
asphalt composition comprising contacting components for an asphalt
composition with an asphalt bio-extender of the present
application.
In a further aspect, the present application discloses a
bio-rejuvenator for asphalt compositions comprising a bio-adhesive
composition as disclosed herein and optionally an asphalt binder.
In another aspect, the present application discloses a method of
rejuvenating asphalt pavement, comprising contacting an asphalt
composition with a bio-rejuvenator as disclosed herein.
In another aspect, the present application discloses a bio-modified
binder comprising a bio-adhesive composition disclosed herein. The
present application also discloses a bio-modified composition
comprising a bio-adhesive composition of the present application
and optionally asphalt, and further optionally wherein the asphalt
is recycled asphalt. In another aspect, the present application
also discloses a rubber-containing bio-asphalt composition
comprising a bio-adhesive composition disclosed herein, rubber and
optionally comprising an asphalt binder and/or an aggregate other
than rubber. In a further aspect, the present application further
discloses a nanoclay-containing bio-asphalt comprising a
bio-adhesive composition as disclosed herein, nanoclay and
optionally comprising an asphalt binder and/or an aggregate other
than nanoclay.
The present application also discloses a method of covering a
surface with a bio-modified asphalt composition, comprising
contacting the surface with such a composition, optionally wherein
the surface is a roof, a road, a floor, a crack or a joint.
Further, the present application discloses a method of sealing a
crack or joint in asphalt pavement comprising applying a
bio-modified composition as disclosed herein.
In one aspect, the present application discloses a method of
isolating a bio-adhesive composition from a bio-oil, the method
comprising: (a) providing a bio-oil derived from animal waste; (b)
distilling the bio-oil to remove a light liquid fraction, wherein
the distilling occurs at a vacuum pressure of between about 1 mm Hg
and about 80 mm Hg while heating at a rate of between about
5.degree. C. per hour and about 50.degree. C. to a temperature of
up to 60.degree. C.; and (c) isolating a bio-adhesive composition
from the bio-oil under conditions such that the viscosity of the
bio-adhesive composition is not allowed to exceed 1 centipoise (cP)
at 135.degree. C. In one embodiment, the animal waste comprises
beef manure, dairy manure, swine manure, sheep manure, poultry
manure or combinations thereof; in one variation, the animal waste
comprises swine manure. In another variation, the animal waste
consists essentially of swine waste. In another embodiment, the
viscosity of the bio-adhesive composition is not allowed to exceed
0.5 cP at 135.degree. C. In another embodiment, the bio-adhesive
composition comprises a heavy liquid fraction and a bio-residue. In
one variation of any of the disclosed aspects or embodiments, the
vacuum pressure is about 3 mm Hg. In another variation, the bio-oil
is treated with a solvent to provide a bio-char; in one
alternative, the bio-char is isolated by filtration. In another
embodiment, the method further comprises using the bio-adhesive
composition as a component of a composition selected from the group
consisting of a bio-adhesion promoter, an asphalt bio-extender, a
bio-rejuvenator, a biomodified binder, and a bio-asphalt. In one
variation, the bio-asphalt is a rubber-containing bio-asphalt or a
nanoclay-containing bio-asphalt.
In another aspect, the present application discloses a method of
isolating a bio-adhesive composition from a bio-oil, the method
comprising: (a) providing a bio-oil derived from animal waste; (b)
distilling the bio-oil to provide a distilled heavy liquid fraction
and a bio-residue that is not distilled, wherein the distilling
occurs under vacuum pressure while heating at a rate of between
about 5.degree. C. per hour and about 50.degree. C. per hour to (1)
a temperature ranging from 60.degree. C. to 100.degree. C., or (2)
a temperature ranging from 100.degree. C. to 160.degree. C.,
wherein the viscosity of the bio-residue is not allowed to exceed 1
cP at 135.degree. C.; and (c) isolating the bio-adhesive
composition comprising the heavy liquid fraction. In one
embodiment, the method further comprises isolating a bio-adhesive
composition comprising the bio-residue. In one variation of any
disclosed aspect or embodiment, the animal waste comprises beef
manure, dairy manure, swine manure, sheep manure, poultry manure or
combinations thereof. In one alternative, the animal waste
comprises swine manure; in another variation, the animal waste
consists essentially of swine waste. In another variation, the
viscosity of the bio-residue is not allowed to exceed 0.5 cP at
135.degree. C. In one embodiment of the methods disclosed herein,
the temperature ranges from 60.degree. C. to 100.degree. C. and the
bio-adhesive composition comprises a heavy liquid fraction
comprising about 10% to about 20% by weight of amide-containing
compounds. In another embodiment of the disclosed methods, the
temperature ranges from 100.degree. C. to 160.degree. C. and the
bio-adhesive composition comprises a heavy liquid fraction
comprising about 1% to about 5% by weight of amide-containing
compounds. In one variation, the methods disclosed herein further
comprise distilling the bio-oil to remove a light liquid fraction,
wherein the distilling occurs at vacuum pressure between about 1 mm
Hg and about 80 mm Hg while heating at a rate of between about
5.degree. C. per hour and about 50.degree. C. to a temperature of
up to 60.degree. C. In yet another variation, the vacuum pressure
is about 3 mm Hg. In one embodiment, the bio-oil is treated with a
solvent to provide a bio-char; in one variation, the bio-char is
isolated by filtration. In one embodiment, the method further
comprises using the bio-adhesive composition as a component of a
composition selected from the group consisting of a bio-adhesion
promoter, an asphalt bio-extender, and a bio-rejuvenator. In
another embodiment, the method further comprises using the
bio-adhesive composition comprising the bio-residue as a component
of a composition selected from the group consisting of a
bio-modified binder and a bio-asphalt. In one variation, the
bio-asphalt is a rubber-containing bio-asphalt or a
nanoclay-containing bio-asphalt.
In one aspect, the present application discloses a bio-adhesive
composition produced by any of the methods disclosed herein. In
another aspect, the present application discloses a bio-adhesive
composition, comprising a heavy liquid fraction and a bio-residue,
wherein the composition has a viscosity of about 0.5 cP at
135.degree. C. wherein said heavy liquid fraction and bio-residue
is isolated from bio-oil produced from animal waste and wherein
said bio-adhesive composition does not contain a light liquid
fraction. In yet another aspect, the present application discloses
a bio-adhesive composition, comprising a heavy liquid fraction
having a viscosity of between about 0.1 cP and 0.5 cP at
135.degree. C., optionally, between about 0.2 cP and about 0.5 cP,
wherein said bio-adhesive composition does not contain a light
liquid fraction. In one variation of any of the disclosed aspects
or embodiments, the bio-adhesive composition comprises a heavy
liquid fraction comprising about 10% to about 20% by weight of
amide-containing compounds, wherein said bio-adhesive composition
does not contain a light liquid fraction. In another variation, the
bio-adhesive composition comprises a heavy liquid fraction
comprising about 1% to about 5% by weight of amide-containing
compounds, wherein said bio-adhesive composition does not contain a
light liquid fraction.
In another aspect, the present application discloses a bio-adhesive
composition, comprising a bio-residue having a viscosity of at
least about 0.4 cP, optionally between about 0.5 cP and 1 cP, at
135.degree. C., wherein said bio-adhesive composition does not
contain a light liquid fraction.
In yet another aspect, the present application discloses a
bio-adhesion promoter comprising any bio-adhesive composition
disclosed herein. In one embodiment, the bio-adhesive composition
comprises at least about 5% by weight amide containing compounds.
In one embodiment, the present application discloses a method of
making bio-modified asphalt composition, comprising contacting
components for an asphalt composition with a bio-adhesion promoter
disclosed herein.
In another aspect, the present application discloses an asphalt
bio-extender comprising a bio-adhesive composition disclosed herein
and optionally an asphalt binder. In one embodiment, the present
application discloses a method of making a bio-modified asphalt
composition, comprising contacting components for an asphalt
composition with an asphalt bio-extender disclosed herein.
In yet another aspect, the present application discloses a
bio-rejuvenator for asphalt compositions, the bio-rejuvenator
comprising a bio-adhesive composition as disclosed herein, and
optionally an asphalt binder. In one embodiment, the application
discloses a method of rejuvenating asphalt pavement, comprising
contacting an asphalt composition with a bio-rejuvenator disclosed
herein.
In another aspect, the present application discloses a bio-modified
binder comprising a bio-adhesive composition disclosed herein and
optionally asphalt. In one variation of any of the disclosed
aspects or embodiments, the asphalt in the bio-modified composition
is recycled asphalt. In another aspect, the present application
discloses a rubber-containing bio-asphalt composition comprising a
bio-adhesive composition disclosed herein, rubber and optionally an
asphalt binder. In yet another aspect, the present application
discloses a nanoclay-containing bio-asphalt comprising a
bio-adhesive composition disclosed herein, nanoclay and optionally
an asphalt binder. In one variation of any of the disclosed aspects
or embodiments, the bio-modified asphalt composition further
comprises an aggregate other than rubber or nanoclay. In one aspect
the present application discloses a method of covering a surface
with a bio-modified asphalt composition, comprising contacting the
surface with a composition disclosed herein. In one variation, the
surface is a roof, a road, a floor, a crack or a joint. In another
aspect, the present application discloses a method of sealing a
crack or joint in asphalt pavement comprising applying a
bio-modified composition as disclosed herein.
Depending on the properties of the components targeted and isolated
according to the methods of the present application as disclosed
herein, a range of industrially useful products can be prepared
including, but not limited to, a fertilizer nutrient, bio-soil
amendment, bio-fuels, a bio-adhesion promoter, an asphalt
bio-extender, an asphalt bio-binder and a bio-asphalt.
EXAMPLES
Materials and Methods
Preparation of Bio-Oil
Bio-oil can be obtained from animal waste according to methods
known to those of skill in the art, including thermochemical
liquefaction ("TCC"), a chemical reforming process using heat and
pressure in the absence of oxygen to break down long-chain organic
compounds into short chain molecules yielding a bio-oil. For
example, swine manure can be converted to bio-oil via TCC under
known conditions, for example at 305.degree. C. at 10.3 MPa at a
residual time of 80 minutes (Ocfemia, K., 2005 "Hydrothermal
Process of Swine Manure to Oil Using a Continuous Reactor System"
Dissertation, University of Illinois at Urbana-Champaign, AAT
3202149).
Beef, dairy, or poultry manure can be converted to bio-oil via
thermochemical liquefaction under known conditions, for example at
350.degree. C., with 15 minute retention time, using CO as process
gas, at a pressure of 2.06 MPa, with the addition of 1 g sodium
carbonate. (Midgett, J. S. 2008 "Assessing A Hydrothermal
Liquefaction Process Using Biomass Feedstocks" Thesis, Louisiana
State University).
In the following examples, thermochemical liquefaction of animal
waste to form bio-oil was conducted using a high-pressure batch
reactor (autoclave). The experimental set-up is rated up to a
working pressure of 34.4 MPa and a working temperature of
500.degree. C. A heavy-duty magnetic drive stirrer was used for
mixing. A type-J thermocouple was fitted into the reactor for
direct temperature measurements of the reaction media. A standard
pressure gauge was used on the reactor head. A temperature
controller was used to control the temperature of the reactor.
Example 1a
Preparation of Bio-Oil from Chicken Manure
Chicken manure slurry retrieved from NC A&T's farm (Greensboro,
N.C., United States of America) was employed. About 1 gallon of
chicken manure slurry, which is typically about 60-80% liquid by
weight, was charged in a 1.5 gallon reactor. Nitrogen gas was used
to purge the reactor three times.
The purged reactor was then heated over the course of .about.2.5
hours to a setting temperature of 340.degree. C., and the pressure
of the autoclave raised to a reaction pressure of about 10.3 MPa.
The setting temperature can alternately be set to between about
280.degree. C. and about 360.degree. C. When run at 340.degree. C.
at 10.3 MPa, the reaction was completed in about 15-20 minutes. The
reactor was cooled to room temperature using a recycled ice-water
cooling coil over the course of at least about 2 hours. After
cooling, the by-product gas was released from the autoclave, and
the pressure in the autoclave reduced to atmospheric pressure.
The reaction mixture, including bio-oil, solid and aqueous phases,
can be removed from the autoclave for subsequent processing and
separation as in Example 2.
Example 1b
Preparation of Bio-Oil from Swine Manure
Swine manure slurry retrieved from lagoons or deep pits on NC
A&T's farm was employed in the following procedure.
About 1 gallon of swine manure slurry, which is typically about
80%-95% liquid by weight, was charged in a 1.5 gallon reactor.
Nitrogen gas was used to purge the reactor three times as an
optional step; alternately, the thermochemical liquefaction can be
run in a semi-closed system, wherein the gaseous reaction products
pressurize the reaction container, thereby decreasing the
concentration of oxygen to negligible levels. The purged reactor
was then heated over the course of .about.2.5 hours to a setting
temperature of 340.degree. C., and the pressure of the autoclave
raised to a reaction pressure of 10.3 MPa. The setting temperature
can alternately be set to between about 280.degree. C. and about
360.degree. C. When run at 340.degree. C. at 10.3 MPa, the reaction
was completed in about 15 minutes. The reactor was cooled to room
temperature using a recycled ice-water cooling coil over the course
of at least about 2 hours. After cooling, the by-product gas was
released from the autoclave, and the pressure in the autoclave
reduced to atmospheric pressure.
The reaction mixture, including bio-oil, solid and aqueous phases,
was removed from the vessel for separation as in Example 2.
Example 2
Isolation of Components from Bio-Oil Produced from Swine Manure
Generally, the components of the bio-oil were isolated via a
step-wise process: The aqueous phase was isolated via filtration as
`black water.` The solid by-product was isolated by adding solvent
(acetone or acetone/toluene mixture) to the sticky residue thereby
dissolving the bio-oil and leaving behind insoluble bio-char,
comprising roughly 10% of the bio-oil. The bio-oil+solvent was then
vacuum distilled at 3 mm Hg with heating at a rate of between
15.degree. C. per hour and 30.degree. C. per hour up to final
distillation temperature of about 160.degree. C. The various
fractions, including solvent, light liquid fraction and the
remaining mixture of a heavy liquid fraction and bio-residue were
isolated as described.
Example 2a
Isolation of Black Water from Bio-Oil
The reaction mixture, including bio-oil, solid and aqueous phases,
from Example 1b was vacuum filtered. The filtrate, referred to as
black water, was isolated and can be used as a soil fertilizer, as
it is rich in agricultural nutrients and does not contain
measureable amounts of pathogens.
Example 2b
Isolation of Bio-Char from Bio-Oil
The sticky residue from the vacuum filtration of Example 2a was
rinsed with 10-50% solvent (either acetone or a 30:70
acetone/toluene mixture) and filtered.
The solid by-product isolated from the filtration, referred to as
"bio-char" generally comprises about 10% of intermediate bio-oil by
weight and can be used in soil amendment.
Example 2c
Isolation of Light Liquid Component from Bio-Oil
The filtrate from Example 2b was placed in a vacuum distillation
apparatus and the pressure in the apparatus was lowered to 3 mm
Hg.
The gaseous fractions of the bio-oil, the solvent (acetone or
acetone/toluene mix) and the Light Liquid Fraction were collected
via vacuum distillation at 3 mm Hg up to a distillation temperature
of 60.degree. C., using a heating rate of 15.degree. C.-30.degree.
C. per hour.
To obtain gasoline and other liquid fuels, the quality of the light
liquid component from the bio-oil of the present application can
been improved by using processes such as fractional distillation,
thermal cracking, hydrogenation and/or other methods familiar to
those of skill in the art.
Example 2d
Isolation of Bio-Residue and Heavy Liquid Fraction
("Bio-Residue+HLF")
After removal of the gaseous components, the solvent and the light
liquid fraction, the remaining pot liquor from Example 2c comprised
a heavy liquid fraction and bio-residue. The viscosity of the
remaining mixture was measured every 10 minutes during distillation
of the Light Liquid Fraction and the viscosity was not allowed to
go above 0.5 cP at 135.degree. C. before the mixture was removed
from the apparatus and isolated.
Example A
Preparation of a Bio-Adhesion Promoter
It has been shown that the bio-adhesive sample from Example 2d has
properties of a bio-adhesion promoter. In particular, the Example
2d sample was combined with petroleum-based asphalt binder at a
proportion of 5%:95% (bio-product: petroleum product) and the
resulting bio-modified binder mixture was then combined with quartz
substrate and subjected to a direct adhesion test (conditioning in
water at 25.degree. C. for 1 hr. or 8 hr.). The results in FIG. 3
demonstrate the higher adhesion strength for the bio-modified
sample.
Without being bound by theory, it is believed that the
bio-adhesives of the present application, such as for example, the
heavy liquid fraction with amide-containing compounds, have polar
ends and a non-polar hydrocarbon tails. When the bio-adhesive is
added to a petroleum-based asphalt binder, the polar ends of the
compounds in the bio-adhesive attach to the aggregates, such as
quartz substrate (polar surfaces) and the non-polar tails attach to
asphalt (non-polar), thereby promoting adhesion between asphalt and
quartz substrate.
Example B
Preparation of an Asphalt Bio-Extender
It has been shown that the bio-adhesive sample from Example 2d has
properties of an asphalt bio-extender. In particular, the
bio-adhesive sample from Example 2d, having a viscosity of 0.5 cP
at 135.degree. C. was added to asphalt base binder PG 64-22 at 2%,
5%, and 10% by weight of the base binder to produce bio-modified
binder. Bio-binder and base binder were heated to 60.degree. C. and
120.degree. C., respectively. The base binder and bio-binder were
mixed thoroughly at shear rate of 3000 rpm for 30 minutes, while
the temperature was kept at 120.degree. C.
The asphalt and bio-modified asphalt samples were evaluated using a
bending beam rheometer (BBR), which measures stiffness and creep
rate at temperatures representative of the lowest pavement
temperature. In the experiment, a constant load is applied at the
center of an asphalt sample for four minutes--the load simulates
the stresses that build up in pavement upon a drop in temperature.
The m-value, as determined by BBR is a measure of how the asphalt
stiffness changes as loads are applied and is the slope of log
stiffness versus log time curve at any time, t.
As shown in FIG. 4, the m-value of virgin asphalt increases due to
the addition of bio-binder, improving binders' stress relaxation
capability, which results in less stress accumulation. At 5% and
10% modification with bio-adhesive, the specimens were too soft to
be tested and their deflections were above the equipment range.
Without being bound by theory, it is expected that the improvement
in low temperature properties of the binder results in reduced low
temperature cracking due to the general reduction in binder
stiffness and increase in m-value. In this way, the addition of a
robust soft bio-binder exemplifies the properties of a
bio-extender. When the refining process for asphalt removes too
much `soft` material, the bio-binder acts as an effective
bio-extender, softening the bio-modified asphalt.
Example C1
Preparation of Bio-Modified Asphalt Binder
The bio-adhesive sample from Example 2d having a viscosity of 0.5
cP at 135.degree. C. was combined with PG52-28 asphalt binder at a
loading of 5% bioadhesive by weight asphalt binder to create
BMB-PG52-28-5. The base binder and bio-binder were mixed thoroughly
at shear rate of 3000 rpm for 30 minutes at 124.degree. C. The
resulting bio-modified binder was compacted at 113.degree. C.
according to standard methods, e.g. AASHTO T 312 (Gyratory
compaction of HMA Mixtures).
To evaluate the effect of the addition of the 5% bio-binder to the
virgin binder, the bio-modified and virgin binders were tested to
determine their rheological properties and performance grade in
accordance with AASHTO R29.
Viscosity testing results indicated that the bio-modified binder
had a reduced viscosity, as compared to the virgin binder. Lower
binder viscosity can lead to a more workable mixture and this
agrees with the mixture workability results which indicated
increased workability for mixtures with the bio-modified binder.
Without being bound by theory it is believed that mixtures produced
with the bio-modified binder release thermal stresses faster than
petroleum-based asphalt binder thereby improving the thermal
characteristics of mixtures designed with the bio-modified
binder.
Example C2
Preparation of Bio-Asphalt Mixture Comprising BMB and RAP
The effect of bio-modified asphalt binder prepared in Example C1
was evaluated in combination with 40% recycled asphalt pavement
(`RAP`) and 60% aggregate comprising 9.5 mm crushed stone, natural
sand, stone sand and stone dust and developed to meet the
requirements for a 9.5 mm Superpave mixture in accordance with
AASHTO M323 "Superpave Volumetric Mix Design" and AASHTO R35
"Superpave Volumetric Design for Hot Mix Asphalt."
The properties of the bio-modified-RAP asphalt were compared to (1)
a control sample comprising PG52-28 asphalt binder mixed with 9.5
mm Superpave Mixture; (2) a sample comprising control of (1)+40%
RAP mixture; and (3) a sample comprising control of (1)+5%
bio-modified asphalt binder prepared in Example C1.
It is well known that improvements observed in asphalt binder
studies are not consistently reflected in asphalt mixtures, because
the added materials and increased number of variables lead to
variations in properties of asphalt mixtures. As shown herein, the
addition of the bio-modified asphalt binder improved low
temperature cracking properties. It also improved the moisture
resistance compared to the control asphalt mixture that did not
contain the bio-binder.
The addition of bio-modified binder reduces the stiffening effects
caused by the introduction of high percentages of reclaimed asphalt
pavement (RAP) in the mixture. FIG. 5A shows a master curve,
characterizing the stiffness of the mixtures over a wide range of
frequencies and temperatures, and demonstrates that the
incorporation of 40% RAP to the control mixture increased its
stiffness. Typically, negative effects are observed when the
stiffness of the mixture gets too high--the mixture can become too
brittle, which may result in thermal cracking. The introduction of
the bio-modified binder decreased the mixture stiffness for both
the control and 40% RAP mixtures as compared to the mixtures
fabricated with PG52-28 binder. This indicated that the
bio-modified binder reduced the stiffening effects caused by the
introduction of high percentages of RAP in the mixture. The data
for the control mixture fabricated with the bio-modified binder
corresponded well with the volumetric data, which showed a
reduction in air voids at the design gyration level, indicating the
mixture is less stiff and easier to compact.
As shown in FIG. 5C, the incorporation of 40% RAP reduced the
workability of the control mixture. This is consistent with the
data in FIG. 5A because the 40% RAP mixture had higher stiffness as
was illustrated in the dynamic modulus master curves of the
mixtures. The addition of the bio-modified binder improved the
workability of the 40% RAP mixture. At temperatures below
280.degree. F. (138.degree. C.) the workability of the control
mixture and the 40% RAP with bio-modified binders were identical,
as illustrated in FIG. 5C. The control mixture with the
bio-modified binder exhibited the lowest torque, consequently, best
workability. As demonstrated herein, the viscosity of the
bio-modified binder was significantly lower than that of the base
non-modified binder; without being bound by theory the reduction in
viscosity may be a contributing factor to the improved
workability.
Example D
Preparation of an Asphalt Bio-Rejuvenator
The data in Example C further demonstrate that the bio-adhesive
sample from Example 2d has properties of an asphalt
bio-rejuvenator.
FIG. 5A, the master curve of dynamic modulus, shows that the
bio-modified binder rejuvenated the 40% RAP mixture to the extent
that its properties were very close to the mixture with no RAP. In
other words, bio-modified binder cancelled out the negative effect
of oxidized RAP on the dynamic modulus of the mixture. As shown in
FIG. 5B, the predicted and measured dynamic modulus, |E*|, the
addition of the bio-modified binder to the composition comprising
40% RAP shifts the dynamic modulus of the composition back to that
of the control composition, comprising 0% RAP.
Without being bound by theory it is believed that the bio-adhesive
sample replaces the `soft, light` compounds that are lost as
asphalt ages, or oxidizes.
Example E
Preparation of Rubber Containing Bio-Asphalt
The bio-adhesive sample from Example 2d having a viscosity of 0.5
cP at 135.degree. C. was used in the preparation of
rubber-containing bio-asphalt as disclosed herein.
Crumb Rubber Gradation
The crumb rubber used for this experiment was obtained from
reRubber LLC of Ontario, Canada. It was processed by ambient means,
giving the sample more size and shape consistency. The mesh size of
the crumb rubber was selected to be 80-200 as typically smaller
particle size requires less reaction time.
Bio Modified Rubber (BMR)
The binder was blended by means of the wet process using crumb
rubber particle sizes passing the No. 50 sieve. Wet process
blending was used to mix 80-200 mesh crumb rubber and petroleum
based binder (PG 64-22) at three percentages of crumb rubber (5%,
10%, and 15%) with one equivalent of the bio-adhesive of Example 2d
(5%) by the weight of the petroleum based binder. The blending was
accomplished by means of a laterally attached oscillating drill.
Shearing was conducted at the speed of 1000 rpm for 30 minutes at
200.degree. C.
To study the temperature susceptibility of each binder, the VTS
values were calculated based on Equation 1:
.function..eta..times..times..function..eta..times..times..function..func-
tion. ##EQU00001##
T1 and T2 are the temperatures of the binder at known points,
.eta.T1 and .eta.T2 are the respected viscosities (cP) of the
binder at those known points. Typically, the magnitude of the VTS
is directly proportional to the temperature susceptibility of the
binder. The results have been plotted for CRM, BMR, and the control
binder in FIG. 6A. As is shown, both BMR and CRM samples have lower
slopes than that of the control binder indicating that the
temperature susceptibility of binder was reduced due the
modification with rubber and bio-binder.
To investigate effects of rubber modification on shear
susceptibility, the `shear susceptibility` (`SS`), defined as the
rate of change of viscosity with the rate of shear, was determined
at different temperatures and plotted for both CMR and BMR in
comparison with the control binder (FIG. 6B). It can be seen that
SS values for both BMR and CRM are higher than those of control
asphalt; this is expected due to the presence of rubber particles.
Typically, when rubber is blended with asphalt, the rubber
particles are swollen by absorption of the asphalt's oily phase
into the polymer chains of crumb rubber to form a gel-like
material. Unlike polymers, which disperse completely in the asphalt
and cause changes in the molecular structure of the asphalt, crumb
rubber keeps its physical shape and behaves as flexible particulate
filler in the binder producing a non-homogeneous nature. This in
turn, gives rise to shear susceptibility due to the movement of
rubber particles relative to each other in the binder matrix.
As shown, CRM has higher shear susceptibility than control asphalt;
the addition of bio-binder to a composition comprising crumb rubber
led to a reduction in shear susceptibility. Without being bound by
theory, the reduction in shear susceptibility can be attributed to
high oily phase of bio-binder which can be easily absorbed by
rubber particles to enhance swelling. This in turn will produce a
gel-like matrix, which is more homogenous and less susceptible to
shear compared to a non-homogeneous matrix of flexible rubber
particles that can easily shear against each other.
Example F
Preparation of Nanoclay-Containing Bio-Asphalt
Materials
The test materials used in this study are virgin asphalt binder PG
58-28 from Gladstone, Mich., United States of America,
nano-modified asphalt binder containing 2% and 4% nano silica and
2% and 4% Closite 30B (all by weight of base asphalt) from Southern
Clay Products, Inc. and the bio-adhesive analogous to Example 2d
(5% by weight of base asphalt), prepared according to Example 2,
except that the thermochemical liquefaction process was run at
360.degree. C. for 15 min at 10.5 MPa. The bio-adhesive was
isolated as described in Example 2.
Fabrication of Asphalt Nano Composite
The nano-modified asphalt materials were prepared using a high
shear mixer. The bitumen was first heated at about 135.degree. C.
until it became fluid in the mixer. Then 2% and 4% nanoclay (by
weight of base binder) was added to the asphalt, and the mixture
was blended at 5,000 rpm for 2 h. The nano-silica asphalt composite
was processed under the same conditions.
Fabrication of Bio-Modified Binder Nanocomposites
The bio-adhesive described above was added to the base asphalt
binder (PG58-28) at a rate of 5% by weight of asphalt binder to
create the bio-modified binder. The blending of base binder and
bio-adhesive was accomplished by means of a shear mixer. Shearing
was conducted at the speed of 1,600 rpm for 30 minutes at
120.degree. C.
The bio-modified binder nanocomposite was prepared by adding 5% of
bio-binder by weight of asphalt binder to base binder (PG58-28),
and blending at 3,000 rpm for 10 min while temperature was kept at
120.degree. C. After 10 min, 2% and 4% by weight of nanoclay and
nanosilica was added to the mixture blending at 5,000 rpm for 20
min with the temperature kept at 120.degree. C.
Rolling Thin Film Oven Short Term Aging Procedure
A Pressure Aging Vessel, conforming to ASTM 6521-08, was used to
perform long term-aging, Rolling Thin Film Oven aging, in
accordance with ASTM D 2872-04.
The addition of bio-binder enhanced the high temperature
performance and improved the aging resistance of nanoparticle
containing asphalt. As shown in FIG. 7A, the aging resistance of
each of the 2% and 4% nanoparticle-containing asphalt decreased
compared to the control binder, based on the calculated viscosity
aging index (VAI), which is calculated by measuring the viscosity
of the sample before and after short term rolling thin film
oven:
.times..times..times..times..times..times..times..times..times..times..ti-
mes..times..times..times. ##EQU00002##
While there was no significant difference between the effectiveness
of nanoclay and nanosilica on the aging of control asphalt, the
addition of bio-binder affected the nanoparticle-containing
asphalts differently. Without being bound by theory, this property
is attributed to higher affinity of bio-binder for silicate layers
in nanoclay giving rise to a degree of exfoliation.
Addition of bio-binder to these asphalts improved the aging
resistance and for the nanoclay-containing asphalts, the viscosity
aging index is on par to the control asphalt. As shown in FIG. 7B,
the addition of 2% nanoclay increased viscosity of the control
binder by 22% on average and the addition of 4% nanoclay increased
it by an average of 36% within the temperature range (120.degree.
C. to 190.degree. C.). The addition of bio-binder to the control
asphalt binder decreased the viscosity by an average of 16%. The
addition of bio-binder to the 2% and the 4% nanoclay samples
increased viscosity by an average of 13% and 57%, respectively.
Example 3
Isolation of Components from Bio-Oil Produced from Animal Waste
In one variation, an apparatus 200 as disclosed in FIG. 2 can be
used for post-processing bio-oil prepared from animal waste
comprising beef, dairy, poultry, sheep, or swine manure or
combinations thereof. In a first processing step, product mixture
204 of bio-char+bio-oil+solvent is added to filtration device 202,
which captures the insoluble bio-char. The bio-oil in solution is
transferred in the direction of arrow A to vacuum distillation
apparatus 206, which is heated by the designated heater 222, at
temperatures in accordance with the methods disclosed herein.
Pressures are monitored with vacuum gauge 208. Solvent 210 is first
driven off, followed by the light liquid fraction 212. The heavy
liquid fraction 214 can be (1) separately collected as an
amide-compound containing fraction and a fraction with a low
concentration of amide-containing products or (2) left in the pot
liquor and collected in combination with the remaining bio-residue.
Each volatile fraction can be condensed in condenser 215 and
isolated from collection tank 224 via condensate drain 234. The
viscosity of the remaining residue is determined based on the level
of torque required to stir the residue, as shown in FIG. 2. The
residue product P flows at higher temperatures, for example at the
terminal distillation temperatures disclosed herein and the
bio-residue product P can be collected by pumping the `liquid` over
an optional dessicator 216 to remove odorous volatile
compounds.
Example 3a
Isolation of Black Water
The reaction mixture, including bio-oil, solid and aqueous phases,
from Example 1b was vacuum filtered, isolating the aqueous phase,
referred to as black water, which contains insignificant quantities
of pathogens and can be used as a fertilizer.
Example 3b
Isolation of Bio-Char
The sticky residue from the vacuum filtration of Example 3a was
rinsed with 10-50% solvent (either acetone or a 30:70
acetone/toluene mixture) and filtered, separating the insoluble
bio-char from the bio-oil in solution in the filtrate.
Example 3c
Isolation of Light Liquid Fraction from Bio-Oil
The filtrate from Example 3b was placed in a vacuum distillation
apparatus and the pressure in the apparatus was lowered to 3 mm
Hg.
The gaseous fractions of the bio-oil, the solvent (acetone or
acetone/toluene mix) and the Light Liquid Fraction were collected
via vacuum distillation at 3 mm Hg using a heating rate of
15.degree. C. to 30.degree. C. per hour up to a distillation
temperature of 60.degree. C.
Example 3d
Isolation of Heavy Liquid Component Containing High Concentration
of Amide Groups from Bio-Oil
The pot liquor from Example 3c was further vacuum distilled at 3 mm
Hg using a heating rate of 15.degree. C. to 30.degree. C. per hour
from 60.degree. C. to 100.degree. C. for collection of the Heavy
Liquid Fraction containing amide compounds.
When the collection of the first heavy liquid fraction was
completed, the condensed sample had a viscosity of about 0.1 cP.
The sample also contained 10-20% amide compounds, as determined by
FT-IR.
This Heavy Liquid Fraction containing amide compounds can be useful
as a bio-adhesion promoter and optionally as a bio-extender or
bio-rejuvenator.
Example 3e
Isolation of Heavy Liquid Component Containing Low Concentration of
Amide Groups from Bio-Oil
The pot liquor from Example 2c was further vacuum distilled at 3 mm
Hg using a heating rate of 15.degree. C. to 30.degree. C. per hour
from 100.degree. C. to 160.degree. C. for collection of the Heavy
Liquid Fraction containing a low concentration of amide
compounds.
When the collection of the second heavy liquid component was
completed, the condensed sample had a viscosity of about 0.1 cP.
The sample contained amide-containing compounds, but at a lower
concentration compared to the fraction of Example 3d.
This Heavy Liquid Fraction containing low amounts of amide
compounds can be useful as a bio-extender or bio-rejuvenator.
Example 3f
Isolation of Bio-Residue
As disclosed herein, the quality of the bio-residue from the vacuum
distillation of the volatile components of the bio-oil is dependent
on a number of factors, including accurate control of distillation
parameters as well as monitoring the viscosity of the residue.
During isolation of the components in Examples 3c to 3e, the
viscosity of the remaining residue was monitored every 10 minutes
and was not allowed to rise above about 0.5 cP at 135.degree. C.
After isolation of the other components disclosed, the remaining
bio-residue was isolated from the distillation apparatus by pouring
the still flowable residue into a collection flask.
The isolated bio-residue can be used in a variety of applications
as disclosed herein.
Example G
Preparation of a Bio-Adhesion Promoter
The heavy liquid component with amide compounds isolated in Example
3d having a viscosity of about 0.1 cP, but optionally having a
viscosity between about 0.1 cP and about 0.3 cP at 135.degree. C.,
can be combined with bitumen at between about 0.1% and about 5% by
weight. Alternately, the heavy liquid component with
amide-containing compounds can be combined with bitumen in amounts
between about 0.5% and about 3% or between about 1% and about
2%.
The bio-modified adhesion promoter improves adhesion properties
compared to virgin bitumen, as measured by a direct adhesion test
of a mixture of bio-modified adhesion promoter and aggregate,
evaluating the change in adhesion due to exposure to room
temperature water. Without being bound by theory, the improved
properties of the bio-modified asphalt are based in part on the
inclusion of the Heavy Liquid Fraction having amide compounds,
which promote adhesion of the asphalt to the aggregate as disclosed
herein.
Example H
Preparation of a Bio-Adhesion Promoter
The heavy liquid fraction isolated in Example 3d having a viscosity
of about 0.1 cP, but optionally having a viscosity between about
0.1 cP and about 0.3 cP at 135.degree. C., can be combined with
bitumen in amounts between about 0.1% and about 10% by weight to
yield industrially useful bio-adhesion promoter. Alternately, the
heavy liquid component with amide-containing compounds can be
combined with bitumen in amounts between about 1% and about 8% or
between about 2% and about 5% or between about 0.5% and about 3% or
between about 1% and 2%.
The bio-modified adhesion promoter improves adhesion properties
compared to virgin bitumen, as measured by a direct adhesion test
of a mixture of bio-modified adhesion promoter and aggregate,
evaluating the change in adhesion due to exposure to room
temperature water.
The bio-adhesion promoter of the present application can be also
used as Warm Mix Additive to 1) allow for reduction of mixing and
compaction temperature; 2) to enhance workability; and 3) to
increase moisture damage resistance. Introduction of bio-adhesive
promoter to bitumen using an in-line blending in the asphalt plant
can enhance workability of the resulting mixture by reducing the
viscosity of the bitumen. Usually the bio-adhesive promoter is
combined at about 1% to about 10% by weight with bitumen, for
example the bio-adhesive component is combined at about 1% or about
2% or about 3% or about 4% or about 5% or about 6% or about 7% or
about 8% or about 9% or about 10% by weight with bitumen.
Example I
Preparation of an Asphalt Bio-Extender
The heavy liquid fraction isolated in either Example 3d or Example
3e, each having a viscosity of about 0.1 cP, but optionally between
about 0.1 cP and about 0.5 cP at 135.degree. C., can each be
combined at between about 1% and about 75% by weight with bitumen
to yield industrially useful asphalt bio-extenders. Typically, the
amount of bio-extender is between about 5% and about 50% by weight
of petroleum-based asphalt.
Without being bound by theory, it is believed that the optimized
viscosity of the Heavy Liquid Fraction with or without
amide-containing compounds enables the fractions to be effective
asphalt bio-extenders. Specifically, the Heavy Liquid Fraction is
incorporated into a RAP/RAS containing asphalt formulation, wherein
the RAP+RAS fraction is between about 30% and about 40%. The
dynamic modulus measurement shows that the dynamic modulus of the
Heavy Liquid Fraction-containing formulation corresponds well to
the control formulation comprising petroleum-based asphalt with no
RAP/RAS.
Example J
Preparation of an Asphalt Bio-Rejuvenator
The heavy liquid fraction isolated in either Example 3d or Example
3e, each having a viscosity of between about 0.1 cP and about 0.5
cP, can each be combined at between about 1% and 50% by weight with
bitumen to yield industrially useful asphalt bio-rejuvenators.
Consistent with the results in Example D, changes to the dynamic
modulus upon addition of the heavy liquid fraction shows that the
bio-adhesive component is an effective bio-rejuvenator and replaces
the `soft, light` compounds that are lost as asphalt ages or
oxidizes.
Example K
Preparation of Bio-Modified Binder (BMB)
The bio-residue isolated in Example 3f having a viscosity of about
0.5 cP, but optionally having a viscosity between about 0.4 cP and
1 cP, at 135.degree. C. is combined with an asphalt binder at
between about 2% and about 10%, typically about 5% by weight, using
a low shear mixer at 100.degree. C. for at least about 20 minutes,
yielding a bio-modified binder having improved properties compared
to a petroleum-based asphalt binder.
Example L
Preparation of Nanoclay-Containing Bio-Asphalt
The bio-residue isolated in Example 3f having a viscosity of about
0.5 cP at 135.degree. C., but optionally having a viscosity between
about 0.4 cP and 1 cP, is combined with between about 4% and about
10% by weight organonanoclay as identified in Example F using a
high shear mixer for 30 minutes at 100.degree. F. yielding a
brittle aging resistant nanoclay containing bio-asphalt.
Example M
Preparation of Rubber-Containing Bio-Asphalt
The bio-residue isolated in Example 3f having a viscosity of 0.5 cP
at 135.degree. C., but optionally having a viscosity between about
0.4 cP and 1 cP, is combined with rubber as identified in Example
E, using a high shear mixer for 1 hour at 100.degree. F., yielding
a flexible stand alone rubber containing bio-asphalt.
Consistent with the results in Example E, the rubber-containing
bioasphalt of the present example demonstrates improved temperature
susceptibility and shear susceptibility compared to the product
made without the bio-residue.
Example N
Use of Bio-Residue with PG Graded Asphalt
The bio-reside isolated in Example 3f having a viscosity of about
0.5 cP, but optionally having a viscosity between about 0.4 cP and
1 cP at 135.degree. C., is combined with PG64-22 (at 2%, 5% or 10%
bio-binder per asphalt binder by weight) to produce bio-modified
binder. Bio-binder and base binder are heated to 60.degree. C. and
120.degree. C., respectively. The base binder and bio-binder are
mixed thoroughly at shear rate of 3000 rpm for 30 minutes, while
the temperature is kept at 120.degree. C.
Example O
Use of Bio-Residue as Bio-Asphalt
The bio-residue isolated in Example 3f having a viscosity of about
0.5 cP, but optionally having a viscosity between about 0.4 cP and
3 cP or between about 0.5 cP and 1 cP at 135.degree. C. can also be
used as a bio-asphalt without any modifications (such as rubber or
nanoclay). Such a bio-asphalt can be used either with or without
addition of petroleum-based asphalt.
The bio-asphalt of the present example demonstrates industrially
useful properties, as tested by BBR and DSR (dynamic shear
rheometer).
Example P
Use of Bioasphalts as Sealant and Crack Filler
The bioasphalts of the present application can also be used in
sealing and filling asphalt concrete pavement cracks. In
particular, bioasphalts including but not limited to pure
bio-asphalt, modified bio-asphalt, and rubber-containing
bioasphalt, are placed into or above cracks, generally to prevent
the intrusion of water and material impurities into the cracks and
to reinforce the pavement adjacent to the cracks.
Example Q
Use of Bio-Asphalt in Roofing
Bio-adhesives of the present application are used in liquid asphalt
roofing, (or `hot mop method`). In this example the bio-asphalt as
prepared in Example 3f, Example K, Example M, Example N, or Example
O is installed by spreading hot bio-asphalt over a roof. After
application of this adhesive to a typically flatter roof, a layer
of decorative rocks is distributed on top of the hot asphalt.
Example R
Use of Bioasphalts as Flooring Bio-Adhesive
Bioasphalts of the present application as prepared in Example 3f,
Example K, Example N and Example O can also be used as a flooring
bio-adhesive. In one aspect, bio-adhesives can replace
petroleum-based adhesives which are used to install a wood floor
over a cement slab. Alternately, the flooring adhesive can be used
as a carpet adhesive. Such products can be evaluated according to
ASTM D6004-04 (2011) "Standard Test Method for Determining Adhesive
Shear Strength of Carpet Adhesives" and ASTM D6005-03 (2009)
"Standard Test Method for Determining Slump Resistance of Carpet
Adhesives."
The patents and publications listed herein describe the general
skill in the art and are hereby incorporated by reference in their
entireties for all purposes and to the same extent as if each was
specifically and individually indicated to be incorporated by
reference. In the case of any conflict between a cited reference
and this specification, the specification shall control. In
describing embodiments of the present application, specific
terminology is employed for the sake of clarity. However, the
invention is not intended to be limited to the specific terminology
so selected. Nothing in this specification should be considered as
limiting the scope of the present invention. All examples presented
are representative and non-limiting. The above-described
embodiments may be modified or varied, without departing from the
invention, as appreciated by those skilled in the art in light of
the above teachings. It is therefore to be understood that, within
the scope of the claims and their equivalents, the invention may be
practiced otherwise than as specifically described.
* * * * *
References